Lavatory Treatment Devices

ABSTRACT

An article or a device comprising a delivery means which includes a non-liquid lavatory treatment material which includes a first air treatment constituent in its composition, and wherein the device also includes an air treatment means particularly where the air treatment means is used to treat the ambient environment in the near vicinity, or in the in the proximity of the lavatory appliance with which the article or device is used. The article or device is useful for providing both a treatment composition to the interior of a lavatory appliance, and in particular to the interior of a toilet bowl when such treatment composition is derived from the non-liquid lavatory treatment material which can be for example: a solid, a gel, or a paste which in addition to the first air treatment constituent also contains one or more treatment constituents from which may formed an aqueous treatment composition when the non-liquid lavatory treatment material is contacted with water, and in particular when contacted with water being flushed through the lavatory appliance.

The present invention relates to improve the lavatory treatment devices, and in particular is directed to articles and devices used to provide a cleaning and/or sanitizing and/or disinfecting treatment to a sanitary appliance, and in particular to a toilet bowl.

In the developed world, toilets and toilet bowls are ubiquitous. While they provide an important sanitary convenience to persons using them, they also require maintenance. Apart from the maintenance of the mechanical operation of the toilet bowl, toilets also require periodic cleaning in order to ensure their cleanliness, and hygienic condition. Frequently a cleaning operation is performed by human action or human intervention. In the most common cleaning operation a human periodically provides a quantity of a treatment composition, such as from a bottle or other dispenser, by manually dispensing said the treatment composition to the interior and exterior surfaces of a toilet bowl. Usually, such an operation is accompanied by manual agitation, e.g., scrubbing or wiping, usually by the use of a toilet brush which can be used to both spread in the treatment composition to surface it is including inclined surfaces of the toilet bowl as well as to the portions of the toilet bowl underneath the interior of the toilet bowl rim wherein hard water stains are known to form. Such an operation however is unpopular in fact it only provides for the periodic cleaning of a toilet bowl or other lavatory appliance, and also requires human intervention. Alternately, a cleaning operation can be performed by providing a lavatory treatment device in the form of a cleansing block which can be supplied either to the supply tank or supply cistern of the toilet bowl within which treatment chemicals provided as part of the cleaning block are dispersed in order to form a liquid treatment composition which then comes into contact with the inner surfaces of the toilet bowl during the flush cycle. Such a cleaning operation utilizing a cleansing block is particularly advantageous from a consumer standpoint to ask, with each flush of the toilet bowl, a quantity of a treatment composition is released to the toilet bowl which often functions to minimize the buildup of stains, as well as assist in the removal of lime scale which is frequently encountered on inner surfaces of toilet bowls particularly where hard water is used as a supply source. The primary consumer to do so where are the fact that the use of such a cleansing block is convenient and requires no human intervention other than that the act of installing a device or article which includes cleansing block, optionally replenishing the device or article with a new cleansing block, and ultimately removing the device or article which includes the cleansing block. Such articles or devices are themselves well known to the art and are in widespread use.

Notwithstanding the benefits of the use of such articles or devices which include cleansing blocks, their use is not without shortcomings. One widely observed shortcoming is the fact that all such articles or devices which include a cleansing block may provide a generally satisfactory cleaning treatment, such requires that the cleansing block be formulated in order to withstand repeated flushings with water in order to import an appreciable and satisfactory service life to the cleansing block. Such dictates that the formulations useful in the formation of cleansing blocks should be on the one hand, sufficiently resistant to the erosion and or dissolution of the cleansing block when contacted with water, yet on the other hand should be sufficiently dissolvable search release effective amounts of cleaning constituents such as one or more surfactants, and the like, into the flush water which comes into contact with the cleansing block contained within the article or device. Such are competing considerations, and typically cleansing blocks are formulated to have a useful service life of at least 14 days, and preferably a least 28 days which unfortunately also limits the selection of constituents which may be used to provide such cleansing blocks and, more significantly limits the effective cleansing ability of the cleansing blocks. Further, the formulation of such cleansing blocks typically dictates the use of constituents which are either primarily provided to provide a cleaning benefit, such as one or more surfactants (tensides), and to control the rate of erosion of the cleansing block in order to ensure that a satisfactory service life is provided. Such limitations this would feed the incorporation of additives, particularly one or more fragrances which may disrupt this delicate balance between cleaning ability and service life, and few of these factors fragrances are frequently omitted from cleansing block compositions. In cleansing block compositions which do include a fragrance constituent, frequently the consumer perception of any fragrance included in the fragrance block is minimal as fragrance constituents would be expected to form only a minor proportion of the overall amount of the constituents use to provide the cleansing block, and due to the limited dissolution or erosion of the cleansing block during the use in a lavatory appliance, it would be expected that very little of a fragrance composition would actually be released with the flush water, and most likely would be entrained in the flush water and flushed away, rather than evaporating or emanating into the ambient environment of the lavatory appliance, e.g., toilet bowl.

The present invention addresses this shortcoming in the art and provides both improved devices and articles as well as processes for the use of such improved devices and articles in conjunction with a lavatory appliance, and particularly in conjunction with a toilet.

In a broad sense the present invention provides an article or a device comprising a delivery means which includes a non-liquid lavatory treatment material which includes a first air treatment constituent in its composition, and wherein the device also includes an air treatment means particularly where the air treatment means is used to treat the ambient environment in the near vicinity, or in the in the proximity of the lavatory appliance with which the article or device is used. The article or device is useful for providing both a treatment composition to the interior of a lavatory appliance, and in particular to the interior of a toilet bowl when such treatment composition is derived from the non-liquid lavatory treatment material which can be for example: a solid, a gel, or a paste which in addition to the first air treatment constituent also contains one or more treatment constituents from which may formed an aqueous treatment composition when the non-liquid lavatory treatment material is contacted with water, and in particular when contacted with water being flushed through the lavatory appliance.

In a further broad sense, the invention also provides an improved process for providing both a cleaning and/or sanitizing and/or disinfecting treatment to a sanitary appliance, and in particular to a toilet bowl and to also treat the ambient environment in the proximity of the sanitary appliance being treated, which contemplates the use of any aspect of the device or apparatus according to the inventive concept, and especially as described herein.

According to first aspect of the invention there is provided a device comprising a delivery means which delivery means includes a non-liquid lavatory treatment material which includes a first air treatment constituent, and which device also includes a further (at least a second) air treatment means containing a further air treatment constituent which is separate from the non-liquid lavatory treatment material which includes the first air treatment constituent for providing a further air treatment constituent to the ambient environment of the device.

According to a second aspect of the invention, the delivery means of the device according to the first aspect of the invention is a cage or container containing a quantity of a non-liquid lavatory treatment material which can be for example: a solid, a gel, or a paste which in addition to the first air treatment constituent also contains one or more treatment constituents, for example, one a more surfactants, wherein an aqueous treatment composition useful for providing a cleaning and/or sanitizing and/or disinfecting benefit to lavatory appliance may be formed by contacting the lavatory treatment material with water.

According to a third aspect of the invention, the delivery means of the device according to the second aspect of the invention is a cage or a container which includes one or more perforations or passages which permit for the entry of, and for the egress of water, and in particular flush water, to pass into the interior of the delivery means and contact the non-liquid lavatory treatment material.

According to a fourth aspect of the invention, the delivery means of the device according to the invention excludes a cage or container.

According to a fifth aspect of the invention there is provided at least one hanger means which may be used to suspend the device according to the invention upon a portion of a sanitary appliance, and especially where the sanitary appliance is a toilet bowl and said portion is a section of a toilet bowl rim.

According to the sixth aspect of the invention there is provided a non-liquid lavatory treatment material according to the first aspect of the invention which includes as a first air treatment constituent and/or as part of the air treatment means one or more constituents selected from: perfumes, fragrances, odor masking constituents, odor counteracting constituents, odor neutralizing constituents, air sanitizing/disinfecting constituents (such as one or more glycols, and in particular triethylene glycol) insecticides, or pesticides.

According to seventh aspect of the invention there is provided a device according to the first aspect of the invention wherein the air treatment means comprises a passive device for the delivery of a second air treatment constituent to the ambient environment.

According to an eighth aspect of the invention there is provided a device according to the first aspect of the invention wherein the air treatment means comprises an active device for the delivery of a second air treatment constituent to the ambient environment.

According to the ninth aspect of the invention there is provided a device according to any prior aspect of the invention described herein, wherein the delivery means positions the non-liquid lavatory treatment material in the path of the flush water provided by the lavatory appliance, and in particular a toilet, and where the delivery means positions the air treatment means outside of the path of the flush water provided by the lavatory appliance.

According to tenth aspect of the invention there is provided a device according to the ninth aspect of the invention wherein the delivery means is within the interior of a toilet bowl, as preferably situated proximate to the interior toilet bowl rim, while the air treatment means is on the exterior of the toilet bowl.

According to an eleventh aspect of the invention there is provided a device according to the first aspect of the invention wherein both the delivery means and the air treatment means are positioned within the interior of a toilet bowl.

According to a twelfth aspect of the invention there is provided a device according to the eleventh aspect of the invention wherein the delivery means and the air treatment means present in a device wherein both the delivery means and the air treatment means are in the path of flushing water, or wherein the delivery means is within the path of flushing water, while the air treatment means is outside of the path of flushing water but within the interior of a toilet bowl.

Further aspects of the invention, include processes for the use of the devices according to the invention are described in further detail hereinbelow, and in particular with reference to the figures provided.

An essential element of the device according to the invention is a non-liquid lavatory treatment material which includes a first air treatment constituent, as well as further constituents which are useful for providing a cleaning and/or sanitizing and/or disinfecting benefit to lavatory appliance may be formed by contacting the said lavatory treatment material with water. The non-liquid lavatory treatment material may be a solid, such as a block, tablet or cake, which can be formed by a number of known techniques such as extrusion, or may be a compressed block, tablet or cake or may be a gel, paste or pasty solid.

By the term “non-liquid lavatory treatment materials” are materials which are distinguishable from “thin liquids”, namely those which have a viscosity of up to 50 cps as measured with a an RVF Brookfield Viscometer, #2 spindle at 20 rpm and 21° C. Preferably the non-liquid lavatory treatment materials are materials which have a viscosity of at least (in order of increasing preference) 500 cps, 750 cps, 1000 cps, 1250 cps, 1500 cps, 1750 cps, 2000 cps as measured under these conditions. In many preferred embodiments the non-liquid lavatory treatment materials are in the form of a solid or compressed tablet, block or cake.

As chemical constituents the non-liquid lavatory treatment materials may include any known art cleaning agents or cleaning constituents known to those of ordinary skill in the relevant art, and without limitation include one or more detersive surfactants selected from anionic, cationic, nonionic as well as amphoteric or zwitterionic surfactants. Certain detersive surfactants may also provide a dual role in providing detergency as well as a disinfecting effect, viz, certain cationic surfactants, which are described hereinafter as a useful disinfecting agent.

Exemplary useful anionic surfactants which may be used in the non-liquid lavatory treatment material of the invention can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric acid reaction products having in their molecular structure an alkyl or alkaryl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the anionic surfactants which can be employed in practicing the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C₈-C₁₈ carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); paraffin sulfonate surfactants having the general formula RSO₃ M, wherein R is a primary or secondary alkyl group containing from about 8 to about 22 carbon atoms (preferably 10 to 18 carbon atoms) and M is an alkali metal, e.g., sodium, lithium or potassium; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from about 8 to about 12 carbon atoms; the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil and sodium or potassium β-acetoxy- or β-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.

A preferred class of anionic surfactants are linear alkyl benzene sulfonate surfactant wherein the alkyl portion contains 8 to 16 carbon atoms, and most preferably about 11 to 13 carbon atoms. According to particularly preferred embodiments of the invention, the solid block compositions necessarily include an anionic surfactant.

A further preferred class of anionic surfactants are alpha olefin sulfonates, as well as salts thereof, e.g., alkali metal salts. Preferred are C₈ through C₂₂ alpha olefin sulfonates, particularly C₁₂ through C₁₈, and especially C₁₄, and C₁₆ alpha olefin sulfonates as well as blends of two or more thereof. According to particularly preferred embodiments of the invention, the solid block compositions necessarily include an alpha olefin sulfonate anionic surfactant.

The detersive surfactant constituent of the solid block composition of the invention may include one or more nonionic surfactants. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with an alkylene oxide, especially ethylene oxide or with the polyhydration product thereof, a polyalkylene glycol, especially polyethylene glycol, to form a water soluble or water dispersible nonionic surfactant compound. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements may various. Exemplary nonionic compounds include the polyoxyethylene ethers of alkyl aromatic hydroxy compounds, e.g., alkylated polyoxyethylene phenols, polyoxyethylene ethers of long chain aliphatic alcohols, the polyoxyethylene ethers of hydrophobic propylene oxide polymers, and the higher alkyl amine oxides.

One class of useful nonionic surfactants include polyalkylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with an alkylene oxide, especially an ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.

A further class of useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of an alkylene oxide, especially an ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms). Other examples are those C₆-C₁₁ straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide. Their derivation is well known in the art. Examples include Alfonic® 810-4.5, which is described in product literature from Sasol as a C₈-C₁₀ straight-chain alcohol having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt. %), and an HLB of about 12; Alfonic® 810-2, which is described in product literature as a C₈-C₁₀ straight-chain alcohols having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt. %), and an HLB of about 12; and Alfonic® 610-3.5, which is described in product literature as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles (about 50 wt. %), and an HLB of 10. Other examples of alcohol ethoxylates are C₁₀ oxo-alcohol ethoxylates available from BASF under the Lutensol® ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol® ON 30; Lutensol® ON 50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70; Lutensol® ON 80; and Lutensol®ON 110). Other examples of ethoxylated alcohols include the Neodol® 91 series non-ionic surfactants available from Shell Chemical Company which are described as C₉-C₁₁ ethoxylated alcohols. The Neodol® 91 series non-ionic surfactants of interest include Neodol® 91-2.5, Neodol® 91-6, and Neodol® 91-8. Neodol® 91-2.5 has been described as having about 2.5 ethoxy groups per molecule; Neodol 91-6 has been described as having about 6 ethoxy groups per molecule; and Neodol 91-8 has been described as having about 8 ethoxy groups per molecule. Further examples of ethoxylated alcohols include the Rhodasurf® DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates. Rhodasurf® DA-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5; Rhodasurf® DA-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5; and Rhodasurf® DA-639 is a 90% solution of DA-630. Further examples of ethoxylated alcohols include those from Tomah Products (Milton, Wis.) under the Tomadol® tradename with the formula RO(CH₂CH₂O)_(n)H where R is the primary linear alcohol and n is the total number of moles of ethylene oxide. The ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8—where R is linear C₉/C₁₀/C₁₁ and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R is linear C₁₁ and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5—where R is linear C₁₂/C₁₃ and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12—where R is linear C₁₂/C₁₃/C₁₄/C₁₅ and n is 3, 7, 9, or 12; and 45-7; 45-13—where R is linear C₁₄/C₁₅ and n is 7 or 13.

A further class of useful nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C₆-C₁₈ alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol. These examples include the Genapol® UD (ex. Clariant, Muttenz, Switzerland) described under the tradenames Genapol® UD 030, C₁₁-oxo-alcohol polyglycol ether with 3 EO; Genapol® UD, 050 C₁₁-oxo-alcohol polyglycol ether with 5 EO; Genapol® UD 070, C₁₁-oxo-alcohol polyglycol ether with 7 EO; Genapol® UD 080, C₁₁-oxo-alcohol polyglycol ether with 8 EO; Genapol® UD 088, C₁₁-oxo-alcohol polyglycol ether with 8 EO; and Genapol® UD 110, C₁₁-oxo-alcohol polyglycol ether with 11 EO.

Exemplary useful nonionic surfactants include the condensation products of a secondary aliphatic alcohols containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are those presently commercially available under the trade name of Tergitol® such as Tergitol 15-S-12 which is described as being C₁₁-C₁₅ secondary alkanol condensed with 9 ethylene oxide units, or Tergitol 15-S-9 which is described as being C₁₁-C₁₅ secondary alkanol condensed with 12 ethylene oxide units per molecule.

A further class of useful nonionic surfactants include those surfactants having a formula:

RO(CH₂CH₂O)_(n)H

wherein; R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C₁₂H₂₅ to C₁₆H₃₃ and n represents the number of ethoxy repeating units and is a number of from about 1 to about 12.

Surfactants of this formula are presently marketed under the Genapol® tradename (ex. Clariant), which surfactants include the “26-L” series of the general formula RO(CH₂CH₂O)_(n)H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C₁₂H₂₅ to C₁₆H₃₃ and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-1,26-L-1.6, 26-L-2,26-L-3,26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% C₁₂ and 45% C₁₄ alcohols, such as 24-L-3,24-L-45, 24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all sold under the Genapol® tradename.

Further useful non-ionic surfactants which may be used in the inventive compositions include those presently marketed under the trade name Pluronics® (ex. BASF). The compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 and preferably 200 to 2,500. The addition of polyoxyethylene radicals of the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble. The molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight. Preferably, these surfactants are in liquid form and particularly satisfactory surfactants are available as those marketed as Pluronics® L62 and Pluronics® L64.

Further nonionic surfactants which may be included in the inventive compositions include alkoxylated alkanolamides, preferably C₈-C₂₄ alkyl di(C₂-C₃ alkanol amides), as represented by the following formula:

R₅—CO—NH—R₆—OH

wherein R₅ is a branched or straight chain C₈-C₂₄ alkyl radical, preferably a C₁₀-C₁₆ alkyl radical and more preferably a C₁₂-C₁₄ alkyl radical, and R₆ is a C₁-C₄ alkyl radical, preferably an ethyl radical.

According to certain particularly preferred embodiments the detersive surfactant constituent necessarily comprises a nonionic surfactant based on a linear primary alcohol ethoxylate particularly wherein the alkyl portion is a C₈ to C₁₆, but particularly a C₉ to C₁₁ alkyl group, and having an average of between about 6 to about 8 moles of ethoxylation.

One further useful class of nonionic surfactants include those in which the major portion of the molecule is made up of block polymeric C₂-C₄ alkylene oxides, with alkylene oxide blocks containing C₃ to C₄ alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain starting group, can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, and secondary alcohols.

One group of nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A):

HO-(EO)_(x)(PO)_(y)(EO)_(z)—  (A)

where

EO represents ethylene oxide,

PO represents propylene oxide,

y equals at least 15,

(EO)_(x+z) equals 20 to 50% of the total weight of said compounds, and,

the total molecular weight is preferably in the range of about 2000 to 15,000.

Another group of nonionic surfactants appropriate for use in the new compositions can be represented by the formula (B):

R-(EO,PO)_(a)(EO,PO)_(a)(EO,PO)_(b)—H  (B)

wherein R is an alkyl, aryl or aralkyl group,

-   -   the alkoxy group contains 1 to 20 carbon atoms, the weight         percent of EO is within the range of 0 to 45% in one of the         blocks a, b, and within the range of 60 to 100% in the other of         the blocks a, b, and the total number of moles of combined EO         and PO is in the range of 6 to 125 moles, with 1 to 50 moles in         the PO rich block and 5 to 100 moles in the EO rich block.

Further nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000.

Still further useful nonionic surfactants containing polymeric butoxy (BO) groups can be represented by formula (C) as follows:

RO—(BO)_(n)(EO)_(x)—H  (C)

wherein R is an alkyl group containing 1 to 20 carbon atoms,

-   -   n is about 15 and x is about 15.

Also useful as the nonionic block copolymer surfactants which also include polymeric butoxy groups are those which may be represented by the following formula (D):

HO-(EO)_(x)(BO)_(n)(EO)_(y)—H  (D)

wherein

-   -   n is about 15,     -   x is about 15 and     -   y is about 15.

Still further useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula:

where

(EO) represents ethoxy,

(PO) represents propoxy,

the amount of (PO)_(x) is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (EO)_(y) is such as to provide about 20% to 90% of the total weight of said compound.

Further useful nonionic surfactants include nonionic amine oxide constituent. Exemplary amine oxides include:

A) Alkyl di (lower alkyl) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. The lower alkyl groups include between 1 and 7 carbon atoms. Examples include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide;

B) Alkyl di (hydroxy lower alkyl) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples are bis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide;

C) Alkylamidopropyl di(lower alkyl) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples are cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and

D) Alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.

Preferably the amine oxide constituent is an alkyl di (lower alkyl) amine oxide as denoted above and which may be represented by the following structure:

wherein each:

R₁ is a straight chained C₁-C₄ alkyl group, preferably both R₁ are methyl groups; and,

R₂ is a straight chained C₈-C₁₈ alkyl group, preferably is C₁₀-C₁₄ alkyl group, most preferably is a C₁₂ alkyl group.

Each of the alkyl groups may be linear or branched, but most preferably are linear. Most preferably the amine oxide constituent is lauryl dimethyl amine oxide. Technical grade mixtures of two or more amine oxides may be used, wherein amine oxides of varying chains of the R₂ group are present. Preferably, the amine oxides used in the present invention include R₂ groups which comprise at least 50% wt., preferably at least 60% wt. of C₁₂ alkyl groups and at least 25% wt. of C₁₄ alkyl groups, with not more than 15% wt. of C₁₆, C₁₈ or higher alkyl groups as the R₂ group.

Still further exemplary useful nonionic surfactants which may be used include certain alkanolamides including monoethanolamides and diethanolamides, particularly fatty monoalkanolamides and fatty dialkanolamides.

A cationic surfactant may be incorporated as a germicide or as a detersive surfactant in the solid block composition of the present invention, particularly wherein a bleach constituent is absent from the non-liquid lavatory treatment material. Cationic surfactants are per se, well known, and exemplary useful cationic surfactants may be one or more of those described for example in McCutcheon's Functional Materials, Vol. 2, 1998; Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 481-541 (1997), the contents of which are herein incorporated by reference. These are also described in the respective product specifications and literature available from the suppliers of these cationic surfactants.

Examples of preferred cationic surfactant compositions useful in the practice of the instant invention are those which provide a germicidal effect to the concentrate compositions, and especially preferred are quaternary ammonium compounds and salts thereof, which may be characterized by the general structural formula:

where at least one of R₁, R₂, R₃ and R₄ is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165. The alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl, long-chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms. The substituents R₁, R₂, R₃ and R₄ may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages. The counterion X may be any salt-forming anion which permits water solubility of the quaternary ammonium complex.

Exemplary quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains either amide, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Other very effective types of quaternary ammonium compounds which are useful as germicides include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.

Preferred quaternary ammonium compounds which act as germicides and which are be found useful in the practice of the present invention include those which have the structural formula:

wherein R₂ and R₃ are the same or different C₈-C₁₂alkyl, or R₂ is C₁₂₋₁₆alkyl, C₈₋₁₈alkylethoxy, C₈₋₁₈alkylphenolethoxy and R₃ is benzyl, and X is a halide, for example chloride, bromide or iodide, or is a methosulfate anion. The alkyl groups recited in R₂ and R₃ may be straight-chained or branched, but are preferably substantially linear.

Particularly useful quaternary germicides include compositions which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the BARDAC®, BARQUAT®, HYAMINE®, LONZABAC®, and ONYXIDE® trademarks, which are more fully described in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product literature from the suppliers identified below. For example, BARDAC® 205M is described to be a liquid containing alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride; didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC® 208M)); described generally in McCutcheon's as a combination of alkyl dimethyl benzyl ammonium chloride and dialkyl dimethyl ammonium chloride); BARDAC® 2050 is described to be a combination of octyl decyl dimethyl ammonium chloride/didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC® 2080)); BARDAC® 2250 is described to be didecyl dimethyl ammonium chloride (50% active); BARDAC® LF (or BARDAC® LF-80), described as being based on dioctyl dimethyl ammonium chloride (BARQUAT® MB-50, MX-50, OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are each described as an alkyl dimethyl benzyl ammonium chloride; BARDAC® 4250 and BARQUAT® 4250Z (each 50% active) or BARQUAT® 4280 and BARQUAT 4280Z (each 80% active) are each described as alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl ethyl benzyl ammonium chloride. Also, HYAMINE® 1622, described as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINE® 3500 (50% actives), described as alkyl dimethyl benzyl ammonium chloride (also available as 80% active (HYAMINE® 3500-80)); and HYMAINE® 2389 described as being based on methyldodecylbenzyl ammonium chloride and/or methyldodecylxylene-bis-trimethyl ammonium chloride. (BARDAC®, BARQUAT® and HYAMINE® are presently commercially available from Lonza, Inc., Fairlawn, N.J.). BTC® 50 NF (or BTC® 65 NF) is described to be alkyl dimethyl benzyl ammonium chloride (50% active); BTC® 99 is described as didecyl dimethyl ammonium chloride (50% active); BTC® 776 is described to be myrisalkonium chloride (50% active); BTC® 818 is described as being octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (available also as 80% active (BTC® 818-80%)); BTC® 824 and BTC® 835 are each described as being of alkyl dimethyl benzyl ammonium chloride (each 50% active); BTC® 885 is described as a combination of BTC® 835 and BTC® 818 (50% active) (available also as 80% active (BTC® 888)); BTC® 1010 is described as didecyl dimethyl ammonium chloride (50% active) (also available as 80% active (BTC® 1010-80)); BTC® 2125 (or BTC® 2125 M) is described as alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride (each 50% active) (also available as 80% active (BTC® 2125 80 or BTC® 2125 M)); BTC® 2565 is described as alkyl dimethyl benzyl ammonium chlorides (50% active) (also available as 80% active (BTC® 2568)); BTC® 8248 (or BTC® 8358) is described as alkyl dimethyl benzyl ammonium chloride (80% active) (also available as 90% active (BTC® 8249)); ONYXIDE® 3300 is described as n-alkyl dimethyl benzyl ammonium saccharinate (95% active). (BTC® and ONYXIDE® are presently commercially available from Stepan Company, Northfield, Ill.) Polymeric quaternary ammonium salts based on these monomeric structures are also considered desirable for the present invention. One example is POLYQUAT®, described as being a 2-butenyldimethyl ammonium chloride polymer.

Preferred quaternary germicides used in the non-liquid lavatory treatment materials are those which are supplied in a solid or powdered form, as such greatly facilitates the manufacture of the non-liquid lavatory treatment materials.

When present in a non-liquid lavatory treatment material, it is preferred that the germicidal cationic surfactant(s) are present in amounts so to dispense at least about 200 parts per million (ppm) in the water flushed into the sanitary appliance, e.g., toilet bowl, or into the water retained in the sanitary appliance at the conclusion of the flush cycle.

Further detersive surfactants which may be included are amphoteric and zwitterionic surfactants which provide a detersive effect. Exemplary useful amphoteric surfactants include alkylbetaines, particularly those which may be represented by the following structural formula:

RN⁺(CH₃)₂CH₂COO⁻

wherein R is a straight or branched hydrocarbon chain which may include an aryl moiety, but is preferably a straight hydrocarbon chain containing from about 6 to 30 carbon atoms. Further exemplary useful amphoteric surfactants include amidoalkylbetaines, such as amidopropylbetaines which may be represented by the following structural formula:

RCONHCH₂CH₂CH₂N⁺(CH₃)₂CH₂COO⁻

wherein R is a straight or branched hydrocarbon chain which may include an aryl moiety, but is preferably a straight hydrocarbon chain containing from about 6 to 30 carbon atoms.

One or more detersive surfactant constituents may be present in the non-liquid lavatory treatment material in any effective amount and generally comprises up to about 60% wt. of the total weight of the non-liquid lavatory treatment material. Preferably detersive surfactant constituents comprise about 10-55% wt., more preferably 20-50% wt. of the non-liquid lavatory treatment material.

Further exemplary chemical constituents may be one or more sanitizing agents or germicides which may be present in the non-liquid lavatory treatment material.

The sanitizing agent can be any sanitizing composition known to those of ordinary skill in the relevant art, and without limitation exemplary sanitizing compositions include materials containing alkyl halohydantoins, alkali metal haloisocyanurates, bleach, essential oils, non-quaternary ammonium based germicidal compounds as well as quaternary ammonium germicidal compounds.

By way of non-limiting example, the non-liquid lavatory treatment material may include a bleach constituent. The bleach constituent is relatively inert in the dry state but, which on contact with water, releases oxygen, hypohalite or a halogen especially chlorine. Representative examples of typical oxygen-release bleaching agents, suitable for incorporation in the non-liquid lavatory treatment material include the alkali metal perborates, e.g., sodium perborate, and alkali metal monopersulfates, e.g., sodium monopersulfates, potassium monopersulfate, alkali metal monoperphosphates, e.g., disodium monoperphosphate and dipotassium monoperphosphate, as well as other conventional bleaching agents capable of liberating hypohalite, e.g., hypochlorite and/or hypobromite, include heterocyclic N-bromo- and N-chloro-cyanurates such as trichloroisocyanuric and tribromoiscyanuric acid, dibromocyanuric acid, dichlorocyanuric acid, N-monobromo-N-mono-chlorocyanuric acid and N-monobromo-N,N-dichlorocyanuric acid, as well as the salts thereof with water solubilizing cations such as potassium and sodium, e.g., sodium N-monobromo-N-monochlorocyanurate, potassium dichlorocyanurate, sodium dichlorocyanurate, as well as other N-bromo and N-chloro-imides, such as N-brominated and N-chlorinated succinimide, malonimide, phthalimide and naphthalimide. Also useful in the non-liquid lavatory treatment material as hypohalite-releasing bleaches are halohydantoins which may be used include those which may be represented by the general structure:

X₁ and X₂ are independently hydrogen, chlorine or bromine; and,

R₁ and R₂ are independently alkyl groups having from 1 to 6 carbon atoms. Examples of halohydantoins include, for example, N,N′-dichloro-dimethyl-hydantoin, N-bromo-N-chloro-dimethyl-hydantoin, N,N′-dibromo-dimethyl-hydantoin, 1,4-dichloro, 5,5-dialkyl substituted hydantoin, wherein each alkyl group independently has 1 to 6 carbon atoms, N-monohalogenated hydantoins such as chlorodimethylhydantoin (MCDMH) and N-bromo-dimethylhydantoin (MBDMH); dihalogenated hydantoins such as dichlorodimethylhydantoin (DCDMH), dibromodimethylhydantoin (DBDMH), and 1-bromo-3-chloro-5,5,-dimethylhydantoin (BCDMH); and halogenated methylethylhydantoins such as chloromethylethylhydantion (MCMEH), dichloromethylethylhydantoin (DCMEH), bromomethylethylhydantoin (MBMEH), dibromomethylethylhydantoin (DBMEH), and bromochloromethylethylhydantoin (BCMEH), and mixtures thereof. Other suitable organic hypohalite liberating bleaching agents include halogenated melamines such as tribromomelamine and trichloromelamine. Suitable inorganic hypohalite-releasing bleaching agents include lithium and calcium hypochlorites and hypobromites. The various chlorine, bromine or hypohalite liberating agents may, if desired, be provided in the form of stable, solid complexes or hydrates, such as sodium p-toluene sulfobromamine trihydrate; sodium benzene sulfochloramine dihydrate; calcium hypobromite tetrahydrate; and calcium hypochlorite tetrahydrate. Brominated and chlorinated trisodium phosphates formed by the reaction of the corresponding sodium hypohalite solution with trisodium orthophosphate (and water, as necessary) likewise comprise useful inorganic bleaching agents for incorporation into the non-liquid lavatory treatment materials.

When present, preferably the bleach constituent is a hypohalite liberating compound and more preferably is a hypohalite liberating compound in the form of a solid complex or hydrate thereof. Particularly preferred are chloroisocynanuric acids and alkali metal salts thereof, preferably potassium, and especially sodium salts thereof. Examples of such compounds include trichloroisocyananuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, and trichloro-potassium dichloroisocynanurate complex. The most preferred chlorine bleach material is sodium dichloroisocyanurate; the dihydrate of this material being particularly preferred.

When present, the bleach constituent may be present in any effective amount and may comprise up to about 90% wt., preferably at least about 0.1-60% wt of the non-liquid lavatory treatment material. More preferably, when present, the bleach constituent comprises about 0.5-50% wt., more preferably at least 1-40% wt. of the non-liquid lavatory treatment material.

Other germicidally effective agents useful as sanitizing agents include sodium dichloroisocyanurate (DCCNa) and sodium dibromoisocyanurate. Further examples of non-quaternary ammonium based sanitizing agents include pyrithiones, dimethyldimethylol hydantoin, methylchloroisothiazolinone/methylisothiazolinone sodium sulfite, sodium bisulfite, imidazolidinyl urea, diazolidinyl urea, benzyl alcohol, 2-bromo-2-nitropropane-1,3-diol, formalin (formaldehyde), iodopropenyl butylcarbamate, chloroacetamide, methanamine, methyldibromonitrile glutaronitrile, glutaraldehyde, 5-bromo-5-nitro-1,3-dioxane, phenethyl alcohol, o-phenylphenol/sodium o-phenylphenol, sodium hydroxymethylglycinate, polymethoxy bicyclic oxazolidine, dimethoxane, thimersal dichlorobenzyl alcohol, captan, chlorphenenesin, dichlorophene, chlorbutanol, glyceryl laurate, halogenated diphenyl ethers, phenolic compounds, mono- and poly-alkyl and aromatic halophenols, resorcinol and its derivatives, bisphenolic compounds, benzoic esters (parabens), halogenated carbanilides, 3-trifluoromethyl-4,4′-dichlorocarbanilide, and 3,3′,4-trichlorocarbanilide. More preferably, the non-cationic antimicrobial agent is a mono- and poly-alkyl and aromatic halophenol selected from the group p-chlorophenol, methyl p-chlorophenol, ethyl p-chlorophenol, n-propyl p-chlorophenol, n-butyl p-chlorophenol, n-amyl p-chlorophenol, sec-amyl p-chlorophenol, n-hexyl p-chlorophenol, cyclohexyl p-chlorophenol, n-heptyl p-chlorophenol, n-octyl p-chlorophenol, o-chlorophenol, methyl o-chlorophenol, ethyl o-chlorophenol, n-propyl o-chlorophenol, n-butyl o-chlorophenol, n-amyl o-chlorophenol, tert-amyl o-chlorophenol, n-hexyl o-chlorophenol, n-heptyl o-chlorophenol, o-benzyl p-chlorophenol, o-benzyl-m-methyl p-chlorophenol, o-benzyl-m, m-dimethyl p-chlorophenol, o-phenylethyl p-chlorophenol, o-phenylethyl-m-methyl p-chlorophenol, 3-methyl p-chlorophenol, 3,5-dimethyl p-chlorophenol, 6-ethyl-3-methyl p-chlorophenol, 6-n-propyl-3-methyl p-chlorophenol, 6-iso-propyl-3-methyl p-chlorophenol, 2-ethyl-3,5-dimethyl p-chlorophenol, 6-sec-butyl-3-methyl p-chlorophenol, 2-iso-propyl-3,5-dimethyl p-chlorophenol, 6-diethylmethyl-3-methyl p-chlorophenol, 6-iso-propyl-2-ethyl-3-methyl p-chlorophenol, 2-sec-amyl-3,5-dimethyl p-chlorophenol 2-diethylmethyl-3,5-dimethyl p-chlorophenol, 6-sec-octyl-3-methyl p-chlorophenol, p-chloro-m-cresol, p-bromophenol, methyl p-bromophenol, ethyl p-bromophenol, n-propyl p-bromophenol, n-butyl p-bromophenol, n-amyl p-bromophenol, sec-amyl p-bromophenol, n-hexyl p-bromophenol, cyclohexyl p-bromophenol, o-bromophenol, tert-amyl o-bromophenol, n-hexyl o-bromophenol, n-propyl-m,m-dimethyl o-bromophenol, 2-phenyl phenol, 4-chloro-2-methyl phenol, 4-chloro-3-methyl phenol, 4-chloro-3,5-dimethyl phenol, 2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-terabromo-2-methylphenol, 5-methyl-2-pentylphenol, 4-isopropyl-3-methylphenol, para-chloro-meta-xylenol, dichloro meta xylenol, chlorothymol, and 5-chloro-2-hydroxydiphenylmethane.

Quaternary ammonium based sanitizing agents include any cationic surfactant which is known or may be found to provide a broad antibacterial or sanitizing function; these have been described above with reference to detersive surfactants.

As a further chemical constituent, the non-liquid lavatory treatment materials of the invention may also comprise a coloring agent which imparts either a color to the non-liquid lavatory treatment material, or to the water in which it comes into contact, but especially which imparts color to the water contained within the sanitary appliance. Where the sanitary appliance is a toilet, desirably the coloring agent imparts a color to the water contained within the cistern, or within the toilet bowl particularly following the flush cycle of a toilet, or may impart a color in both locations. Such coloring agents have great consumer appeal, and indeed any known art coloring agent may be provided in any effective amount in order to impart a coloring effect. Colorants, especially dyes, are preferred when formulated as dry powders to enable direct incorporation into the non-liquid lavatory treatment materials of the invention, however, liquid colorants may be employed in conjunction with suitable carriers. Useful colorants include any materials which may provide a desired coloring effect. Exemplary useful coloring agents include dyes, e.g., Alizarine Light Blue B (C.I. 63010), Carta Blue VP(C.I. 24401), Acid Green 2G (C.I. 42085), Astragon Green D (C.I. 42040) Supranol Cyanine 7B (C.I. 42675), Maxilon Blue 3RL (C.I. Basic Blue 80), acid yellow 23, acid violet 17, a direct violet dye (Direct violet 51), Drimarine Blue Z-RL (C.I. Reactive Blue 18), Alizarine Light Blue H-RL (C.I. Acid Blue 182), FD&C Blue No. 1, FD&C Green No. 3 and Acid Blue No. 9. When a bleach constituent is included in the non-liquid lavatory treatment material, the colorant, e.g., dye, should be selected so to ensure the compatibility of the colorant with the bleach constituent, or so that its color persists despite the presence in the toilet bowl of a concentration of hypochlorite which is effective to maintain sanitary conditions. Frequently however, a non-liquid lavatory treatment material which includes a bleach constituent do not comprise any colorants. Desirably the colorants, when present, do not exceed 15% wt. of the non-liquid lavatory treatment material, although generally lesser amounts are usually effective. When present, colorants are desirably present in an amount from about 0.1 to 15 percent of the total weight of the chemical composition.

As an essential constituent, the non-liquid lavatory treatment materials necessarily include a first air treatment constituent which may be one or more constituents, which by way of non-limiting example, include: perfumes, fragrances, odor masking constituents, odor counteracting constituents, odor neutralizing constituents, air sanitizing/disinfecting constituents (such as one or more glycols, and in particular triethylene glycol,) insecticides, or pesticides

The fragrance may be any composition which is known to the art to provide a perceptible fragrancing benefit, any may be based on naturally occurring materials such as one or more essential oils, or may be based on synthetically produced compounds as well. Examples of essential oils include pine oil, Anetlhole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Perui), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Bomneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Canaga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Counmarin 69° C. (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil, L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), and Wintergreen oil.

Many of these essential function as a fragrance agent, which fragrance agent which may be a substance or mixture of various substances including those which are naturally derived (i.e., obtained by extraction of flower, herb, blossom or plant), those which are artificially derived or produced (i.e., mixture of natural oils and/or oil constituents), and those which are synthetically produced substances (odiferous substances). Generally fragrance agents are complex mixtures or blends various organic compounds including, but not limited to, certain alcohols, aldehydes, ethers, alamatic compounds and varying amounts of essential oils such as from about 0 to about 25% by weight, usually from about 0.05 to about 12% by weight, the essential oils themselves being volatile odiferous compounds and also functioning to aid in the dissolution of the other components of the fragrance agent. In the present invention, the precise composition of the fragrance agent desirably emanates a pleasing fragrance, but the nature of the fragrance agent is not critical to the success of the invention.

Additionally the first air treatment constituent may also be any other material which is useful in providing treatment of ambient air, such as a sanitizing agent. e.g., one or more glycols or alcohols, particularly triethylene glycol, or one or more materials which are intended to counteract, neutralize, or mask odors in the absence of, or in conjunction with a fragrance or perfume composition, as well as may be one or more materials which provide an effective insecticide repelling or insecticidal benefit; such would be particularly useful in climates or environments where insects present a nuisance or health hazard.

As further chemical constituents, the non-liquid lavatory treatment materials of the invention may comprise an anti-limescale agent, which can be generally classified as a cleaning agent in that it provides a cleaning effect to treated lavatory device surfaces. The anti-limescale agent can virtually any known anti-limescale agent compositions known to those of ordinary skill in the relevant art. For example, compositions containing anionic and/or nonionic surfactants together with typical anti-limescale agents, for example, amidosulfonic acid, bisulfate salts, organic acids, organic phosphoric salts, alkali metal polyphosphates, and the like. Examples of anti-limescale agent compositions can be found in, for example, U.S. Pat. Nos. 5,759,974; 4,460,490; and 4,578,207, the contents of which are herein incorporated by reference. Further examples of anti-limescale agents include organic acids (for example, citric acid, lactic acid, adipic acid, oxalic acid and the like), organic phosphoric salts, alkali metal polyphosphates, sulfonic, and sulfamic acids and their salts, bisulfate salts, EDTA, phosphonates, and the like.

The non-liquid lavatory treatment materials may comprise stain inhibiting materials. The solid block composition of the invention may, for example, include an effective amount of a manganese stain inhibiting agent which is advantageously included wherein the sanitary appliance is supplied by a water source having an appreciable or high amount of manganese. Such water containing a high manganese content are known to frequently deposit unsightly stains on surfaces of sanitary appliances, especially when the solid block composition also contains a bleach source which provides a hypochlorite. To counteract such an effect the solid block composition of the present invention may comprise a manganese stain inhibiting agent, such as a partially hydrolyzed polyacrylamide having a molecular weight of about 2000 to about 10,000, a polyacrylate with a molecular weight of about 2000 to about 10,000, and/or copolymers of ethylene and maleic acid anhydride with a molecular weight of from about 20,000 to about 100,000. When present the satin inhibiting materials may comprise to about 10% wt. of the weight of the non-liquid lavatory treatment material.

The non-liquid lavatory treatment materials of the invention may include one or more preservatives. Such preservatives are primarily included to reduce the growth of undesired microorganisms within the non-liquid lavatory treatment material during storage prior to use or while used, although it is expected that the such a preservative may impart a beneficial antimicrobial effect to the water in the sanitary appliance to which the treatment block is provided. Exemplary useful preservatives include compositions which include parabens, including methyl parabens and ethyl parabens, glutaraldehyde, formaldehyde, 2-bromo-2-nitropropoane-1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3-one, and mixtures thereof. One exemplary composition is a combination 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one where the amount of either component may be present in the mixture anywhere from 0.001 to 99.99 weight percent, based on the total amount of the preservative. For reasons of availability, the most preferred preservative are those commercially available preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one marketed under the trademark KATHON® CG/ICP as a preservative composition presently commercially available from Rohm and Haas (Philadelphia, Pa.). Further useful preservative compositions include KATHON® CG/ICP II, a further preservative composition presently commercially available from Rohm and Haas (Philadelphia, Pa.), PROXEL® which is presently commercially available from Zeneca Biocides (Wilmington, Del.), SUTTOCIDE® A which is presently commercially available from Sutton Laboratories (Chatam, N.J.) as well as TEXTAMER® 38AD which is presently commercially available from Calgon Corp. (Pittsburgh, Pa.). When present, the optional preservative constituent should not exceed about 5% wt. of the solid block composition, although generally lesser amounts are usually effective.

The inventive non-liquid lavatory treatment materials may include a binder constituent. The binder may function in part controlling the rate of dissolution of the tablet. The binder constituent may be a clay, but preferably is a water-soluble or water-dispersible gel-forming organic polymer. The term “gel-forming” as applied to this polymer is intended to indicate that on dissolution or dispersion in water it first forms a gel which, upon dilution with further water, is dissolved or dispersed to form a free-flowing liquid. The organic polymer serves essentially as binder for the tablets produced in accordance with the invention although, as will be appreciated, certain of the polymers envisaged for use in accordance with the invention also have surface active properties and thereby serve not only as binders but also enhance the cleansing ability of the tablets of the invention. Further certain organic polymers, such as substituted celluloses, also serve as soil antiredeposition agents. A wide variety of water-soluble organic polymers are suitable for use in the solid block composition of the present invention. Such polymers may be wholly synthetic or may be semi-synthetic organic polymers derived from natural materials. Thus, for example, on class of organic polymers for use in accordance with the invention are chemically modified celluloses such as ethyl cellulose, methyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, and hydroxyethyl cellulose. Another class of organic polymers which may be used include naturally derived or manufactured (fermented) polymeric materials such as alginates and carageenan. Also, water-soluble starches and gelatin may be used as the optional binder constituent. The cellulose based binders are a preferred class of binders for use in the solid block composition and may possess the property of inverse solubility that is their solubility decreases with increasing temperature, thereby rendering the tablets of the invention suitable for use in locations having a relatively high ambient temperature.

The optional binder constituent may also be one or more synthetic polymers e.g, polyvinyl alcohols; water-soluble partially hydrolyzed polyvinyl acetates; polyacrylonitriles; polyvinyl pyrrolidones; water-soluble polymers of ethylenically unsaturated carboxylic acids, such as acrylic acid and methacrylic acid, and salts thereof; base-hydrolysed starch-polyacrylonitrile copolymers; polyacrylamides; ethylene oxide polymers and copolymers; as well as carboxypolymethylenes.

In the case of the organic polymeric binders it may be noted that, in general, the higher the molecular weight of the polymer the greater the in-use life of the treatment block of the invention. When present, the total binder content may comprise up to 75% wt. of the solid block composition, but preferably is from 0.5 to 70% by weight, preferably from 1 to 65% by weight, more preferably from 5 to 60% by weight.

The non-liquid lavatory treatment materials may optionally include one or more dissolution control agents. Such dissolution control agent are materials which provide a degree of hydrophobicity to a treatment block formed from the non-liquid lavatory treatment materials whose presence contributes to the slow uniform dissolution of the treatment block when contacted with water, and simultaneously the controlled release of the active constituents such a solid block formed from the non-liquid lavatory treatment materials. Preferred for use as the dissolution control agents are mono- or di-alkanol amides derived from C₈-C₁₆ fatty acids, especially C₁₂-C₁₄ fatty acids having a C₂-C₆ monoamine or diamine moiety. When included the dissolution control agent may be included in any effective amount, but desirably the dissolution control agent is present in an amount not to exceed about 600% wt. of the non-liquid lavatory treatment materials, although generally lesser amounts are usually effective. Generally wherein the non-liquid lavatory treatment material is to be used in an ITB (“in the bowl”) article or device the dissolution control agent is present to about 12% wt., more preferably is present from 0.1-10% wt. and most preferably is present from about 3-8% wt. of the non-liquid lavatory treatment material.

The non-liquid lavatory treatment material may optionally include one or more water-softening agents or one or more chelating agents, for example inorganic water-softening agents such as sodium hexametaphosphate or other alkali metal polyphosphates or organic water-softening agents such as ethylenediaminetetraacetic acid and nitrilotriacetic acid and alkali metal salts thereof. When present, such water-softening agents or chelating agents should not exceed about 20% wt. of the solid block composition, although generally lesser amounts are usually effective.

The non-liquid lavatory treatment material may optionally include one or more solid water-soluble acids or acid-release agents such as sulfamic acid, citric acid or sodium hydrogen sulfate. When present, such solid water-soluble acids or acid-release agents should not exceed about 20% wt. of the solid block composition, although generally lesser amounts are usually effective.

The non-liquid lavatory treatment materials may include diluent materials may be included to provide additional bulk of the product solid block composition and may enhance leaching out of the surfactant constituent when the solid block composition is placed in water. Exemplary diluent materials include any soluble inorganic alkali, alkaline earth metal salt or hydrate thereof, for example, chlorides such as sodium chloride, magnesium chloride and the like, carbonates and bicarbonates such as sodium carbonate, sodium bicarbonate and the like, sulfates such as magnesium sulfate, copper sulfate, sodium sulfate, zinc sulfate and the like, borax, borates such as sodium borate and the like, as well as others known to the art but not particularly recited herein. Exemplary organic diluents include, inter alia, urea, as well as water soluble high molecular weight polyethylene glycol and polypropylene glycol. When present, such diluent materials should not exceed about 80% wt. of the non-liquid lavatory treatment material, although generally lesser amounts are usually effective.

The non-liquid lavatory treatment materials, and particularly lavatory treatment blocks formed therefrom may include one or more fillers. Such fillers are typically particulate solid water-insoluble materials which may be based on inorganic materials such as talc or silica, particulate organic polymeric materials such as finely comminuted water insoluble synthetic polymers. When present, such fillers should not exceed about 30% wt. of the non-liquid lavatory treatment material, although generally lesser amounts are usually effective.

Preferably when formed as a solid block the non-liquid lavatory treatment materials formed into such a solid block includes silica. Silica has been observed to aid in the controlling the rate of dissolution of the non-liquid lavatory treatment material when provided as compressed solid blocks.

The non-liquid lavatory treatment material and treatment blocks formed therefrom may include one or more further processing aids. For example, the solid block composition may also include other binding and/or plasticizing ingredients serving to assist in the manufacture thereof, for example, polypropylene glycol having a molecular weight from about 300 to about 10,000 in an amount up to about 20% by weight, preferably about 4% to about 15% by weight of the mixture may be used. The polypropylene glycol reduces the melt viscosity, acts as a demolding agent and also acts to plasticize the block when the composition is prepared by a casting process. Other suitable plasticizers such as pine oil fractions, d-limonene, dipentene and the ethylene oxide-propylene oxide block copolymers may be utilized. Other useful processing aids include tabletting lubricants such as metallic stearates, stearic acid, paraffin oils or waxes or sodium borate which facilitate in the formation of the treatment blocks in a tabletting press or die.

One advantageously utilized processing aid is a diester constituent which may be represented by the following structure:

wherein: R¹ and R² can independently be C₁-C₆ alkyl which may optionally substituted, Y is (CH₂)_(x), wherein x is 0-10, but is preferably 1-8, and while Y may be a linear alkyl or phenyl moiety, desirably Y includes one or more oxygen atoms and/or is a branched moiety.

Exemplary diester constituents include the following diester compounds according to the foregoing structure: dimethyl oxalate, diethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, diisobutyl oxalate, dimethyl succinate, diethyl succinate, diethylhexyl succinate, dimethyl glutarate, diisostearyl glutarate, dimethyl adipate, diethyl adipate, diisopropyl adipate, dipropyl adipate, dibutyl adipate, diisobutyl adipate, dihexyladipate, di-C₁₂₋₁₅-alkyl adipate, dicapryl adipate, dicetyl adipate, diisodecyl adipate, diisocetyl adipate, diisononyl adipate, diheptylundecyl adipate, ditridecyl adipate, diisostearyl adipate, diethyl sebacate, diisopropyl sebacate, dibutyl sebacate, diethylhexylsebacate, diisocetyl dodecanedioate, dimethyl brassylate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate.

Preferred diester constituents include those wherein Y is —(CH₂)_(x)— wherein x has a value of from 0-6, preferably a value of 0-5, more preferably a value of from 1-4, while R¹ and R² are C₁-C₆ alkyl groups which may be straight chained alkyl but preferably are branched, e.g, iso- and tert-moieties. Particularly preferred diester compounds are those in which the compounds terminate in ester groups.

A further advantageously utilized processing aid is a hydrocarbon solvent constituent. The hydrocarbon solvents are immiscible in water, may be linear or branched, saturated or unsaturated hydrocarbons having from about 6 to about 24 carbon atoms, preferably comprising from about 12 to about 16 carbon atoms. Saturated hydrocarbons are preferred, as are branched hydrocarbons. Such hydrocarbon solvents are typically available as technical grade mixtures of two or more specific solvent compounds, and are often petroleum distillates. Nonlimiting examples of some suitable linear hydrocarbons include decane, dodecane, decene, tridecene, and combinations thereof. Mineral oil is one particularly preferred form of a useful hydrocarbon solvent. Further preferred hydrocarbon solvents include paraffinic hydrocarbons including both linear and branched paraffinic hydrocarbons. The former are commercially available as NORPAR solvents (ex. ExxonMobil Corp.) while the latter are available as ISOPAR solvents (ex. ExxonMobil Corp.) Mixtures of branched hydrocarbons especially as isoparaffins form a further particularly preferred form of a useful hydrocarbon solvent of the invention. Particularly useful technical grade mixtures of isoparaffins include mixtures of isoparaffinic organic solvents having a relatively narrow boiling range. Examples of these commercially available isoparaffinic organic solvents include ISOPAR C described to be primarily a mixture of C₇-C₈ isoparaffins, ISOPAR E described to be primarily a mixture of C₈-C₉ isoparaffins, ISOPAR G described to be primarily a mixture of C₁₀-C₁₁ isoparaffins, ISOPAR H described to be primarily a mixture of C₁₁-C₁₂ isoparaffins, ISOPAR J, ISOPAR K described to be primarily a mixture of C₁₁-C₁₂ isoparaffins, ISOPAR L described to be primarily a mixture of C₁₁-C₁₃ isoparaffins, ISOPAR M described to be primarily a mixture of C₁₃-C₁₄ isoparaffins, ISOPAR P and ISOPAR V described to be primarily a mixture of C₁₂-C₂₀ isoparaffins.

When present such further processing aids are typically included in amounts of up to about 30% by weight, preferably to 20% wt. of a solid block composition formed from the non-liquid treatment material although generally lesser amounts are usually effective.

The non-liquid lavatory treatment materials may comprise include a film forming constituent, viz., a film forming polymer in an effective amount. Such are advantageously present when the non-liquid lavatory treatment materials are in the form of a tablet, cake or a block, although such may also be present when the non-liquid lavatory treatment composition is in the form of a gel or a paste. The use of film forming constituent is believed to provide for a reduction in limescale deposition on the treated hard surfaces, as the film forming constituent is provided with each flush or wash of water passing around such treatment block. It is believed that the long term buildup of limescale may be resisted or retarded on hard surfaces, viz., lavatory surfaces and lavatory appliances due to the presence of the film-forming constituent thereon. While it is preferred that the film forming constituent deposit a generally continuous film on a hard surface, it is to be understood that while the film forming constituent need be present in the present inventive compositions it is not required that any layer or film formed therefrom which is formed on the surface of a lavatory appliance, e.g., toilet bowl, be necessarily uniform either in thickness or be a continuous film providing uninterrupted surface coverage although such would be preferred. Rather it is contemplated that film forming materials useful in the present invention need not form a continuous or uniform coating, as it is only required that the film forming materials provide some extent of a surface coating to a hard surface upon which it is applied. It is to be understood that the potential for forming the film layer from a film forming composition is influenced by several factors, inter alia, the nature of the hard surface being treated, the geometry and configuration of the hard surface being treated, the fluid dynamics of the water contacting the treatment block, the quality of the water contacting the treatment block.

The film-forming constituent may be present in any amount which is found effective in forming a film on a hard surface being treated. It will be understood that this such a minimum amount will vary widely, and is in part dependent upon the molecular weight of the film forming polymer utilized in a formulation, but desirably at least about 0.001% wt. should be present. More preferably the film forming polymer comprises from 0.001% wt. to 10% wt. of the non-liquid lavatory treatment material compositions of which it forms a part. The identity of particularly preferred film-forming polymers and preferred amounts are disclosed in one or more of the following examples.

Exemplary materials useful in the film forming constituent include film forming polymers such as:

a polymer having the formula

in which n represents from 20 to 99 and preferably from 40 to 90 mol %, m represents from 1 to 80 and preferably from 5 to 40 mol %; p represents 0 to 50 mol, (n+m+p=100); R₁ represents H or CH₃; y represents 0 or 1; R₂ represents —CH₂—CHOH—CH₂— or C_(x)H_(2x) in which x is 2 to 18; R₃ represents CH₃, C₂H₅ or t-butyl; R₄ represents CH₃, C₂H₅ or benzyl; X represents Cl, Br, I, 1/2SO₄, HSO₄ and CH₃SO₃; and M is a vinyl or vinylidene monomer copolymerisable with vinyl pyrrolidone other than the monomer identified in [ ]_(m);

quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate;

polyvinylpyrrolidone;

vinylpyrrolidone/vinylacetate;

vinylpyrrolidone/vinyl caprolactam/ammonium derivative terpolymer, especially where the ammonium derivative monomer has 6 to 12 carbon atoms and is selected from diallylamino alkyl methacrylamides, dialkyl dialkenyl ammonium halides, and a dialkylamino alkyl methacrylate or acrylate;

high molecular weight polyethylene glycol;

water soluble polyethylene oxide;

polyvinylcaprolactam;

polyvinylalcohol;

cationic cellulose polymer;

cationic fatty quaternary ammonium compounds;

organosilicone quaternary ammonium compounds;

2-propenamide, N-[3-(dimethylamino)propyl]-2-methyl, polymer with 1-ethenyl-2-pyrrolidone hydrochloride;

polynitrogen compounds, including amphoteric polyamide polymers; and,

maleic acid/polyolefin copolymers;

one or more of which may be present in effective amounts.

A first film-forming polymer contemplated to be useful in the present compositions is one having the formula

are more fully described in U.S. Pat. No. 4,445,521, U.S. Pat. No. 4,165,367, U.S. Pat. No. 4,223,009, U.S. Pat. No. 3,954,960, as well as GB 1,331,819, the contents of which are hereby incorporated by reference.

The monomer unit within [ ]_(m) is, for example, a di-lower alkylamine alkyl acrylate or methacrylate or a vinyl ether derivative. Examples of these monomers include dimethylaminomethyl acrylate, dimethylaminomethyl methacrylate, diethylaminomethyl acrylate, diethylaminomethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, dimethylaminoamyl methacrylate, diethylaminoamyl methacrylate, dimethylaminohexyl acrylate, diethylaminohexyl methacrylate, dimethylaminooctyl acrylate, dimethylaminooctyl methacrylate, diethylaminooctyl acrylate, diethylaminooctyl methacrylate, dimethylaminodecyl methacrylate, dimethylaminododecyl methacrylate, diethylaminolauryl acrylate, diethylaminolauryl methacrylate, dimethylaminostearyl acrylate, dimethylaminostearyl methacrylate, diethylaminostearyl acrylate, diethylaminostearyl methacrylate, di-t-butylaminoethyl methacrylate, di-t-butylaminoethyl acrylate, and dimethylamino vinyl ether.

Monomer M, which can be optional (p is up to 50) can comprise any conventional vinyl monomer copolymerizable with N-vinyl pyrrolidone. Thus, for example, suitable conventional vinyl monomers include the alkyl vinyl ethers, e.g., methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, etc.; acrylic and methacrylic acid and esters thereof, e.g., methacrylate, methyl methacrylate, etc.; vinyl aromatic monomers, e.g., styrene, a-methyl styrene, etc; vinyl acetate; vinyl alcohol; vinylidene chloride; acrylonitrile and substituted derivatives thereof; methacrylonitrile and substituted derivatives thereof; acrylamide and methacrylamide and N-substituted derivatives thereof; vinyl chloride, crotonic acid and esters thereof; etc. Again, it is noted that such optional copolymerizable vinyl monomer can comprise any conventional vinyl monomer copolymerizable with N-vinyl pyrrolidone. These film-forming polymers of the present invention are generally provided as a technical grade mixture which includes the polymer dispersed in an aqueous or aqueous/alcoholic carrier. Such include materials which are presently commercially available include quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate sold as Gafquat® copolymers (ex. ISP Corp., Wayne, N.J.) which are available in a variety of molecular weights.

Further exemplary useful examples of the film-forming polymers of the present invention include quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate as described in U.S. Pat. No. 4,080,310, to Ng, the contents of which are herein incorporated by reference. Such quaternized copolymers include those according to the general formula:

wherein “x” is about 40 to 60. Further exemplary useful copolymers include copolymers of vinylpyrrolidone and dimethylaminoethylmethacrylate quaternized with diethyl sulphate (available as Gafquat® 755 ex., ISP Corp., Wayne, N.J.).

Such a further useful film-forming polymer according to the invention is a quaternized polyvinylpyrrolidone/dimethylaminoethylmethacrylate copolymer which is commercially available as Gafquat® 734, is disclosed by its manufacturer to be:

wherein x, y and z are at least 1 and have values selected such that the total molecular weight of the quaternized polyvinylpyrrolidone/dimethylamino ethylmethacrylate copolymer is at least 10,000 more desirably has an average molecular weight of 50,000 and most desirably exhibits an average molecular weight of 100,000. A further useful, but less preferred quaternized polyvinylpyrrolidone/dimethylamino ethylmethacrylate copolymer is available as Gafquat® 755N which is similar to the Gafquat® 734 material describe above but has an average molecular weight of about 1,000,000. These materials are sometimes referred to as “Polyquaternium-11”.

Exemplary polyvinylpyrrolidone polymers useful in the present inventive compositions exhibit a molecular weight of at least about 5,000, with a preferred molecular weight of from about 6,000-3,000,000.

Such polyvinylpyrrolidone polymers are generally provided as a technical grade mixture of polyvinylpyrrolidone polymers within approximate molecular weight ranges.

Exemplary useful polyvinylpyrrolidone polymers are available in the PVP line materials (ex. ISP Corp.) which include PVP K 15 polyvinylpyrrolidone described as having molecular weight in the range of from 6,000-15,000; PVP-K 30 polyvinylpyrrolidone with a molecular weight in the range of 40,000-80,000; PVP-K 60 polyvinylpyrrolidone with a molecular weight in the range of 240,000-450,000; PVP-K 90 polyvinylpyrrolidone with a molecular weight in the range of 900,000-1,500,000; PVP-K 120 polyvinylpyrrolidone with a molecular weight in the range of 2,000,000-3,000,000.

Other suppliers of polyvinylpyrrolidone include AllChem Industries Inc, Gainesville, Fla., Kraft Chemical Co., Melrose Park, Ill., Alfa Aesar, a Johnson Matthey Co., Ward Hill, Mass., and Monomer-Polymer & Dajac Labs Inc., Feasterville, Pa.

Exemplary vinylpyrrolidone/vinylacetate copolymers which find use in the present inventive compositions as the film forming constituent vinylpyrrolidone/vinylacetate copolymers comprised of vinylpyrrolidone monomers which may be represented by the following structural formula:

and vinylacetate monomers which may be represented by the following structural formula:

which are usually formed by a free-radical polymerization reaction to produce linear random vinylpyrrolidone/vinylacetate copolymers. The resultant vinylpyrrolidone/vinylacetate copolymers may comprise varying amounts of the individual vinylpyrrolidone monomers and vinylacetate monomers, with ratios of vinylpyrrolidone monomer to vinylacetate monomers from 30/70 to 70/30. The values of x and y in the structural formula should have values such that x+y=100 to 500, preferably x+y=150 to 300. Such values correspond to provide vinylpyrrolidone/vinylacetate copolymers having a total molecular weight in the range from about 10,000 to about 100,000, preferably from about 12,000 to about 60,000. Alternately, desirably the ratio of x:y is 0.1:4.0, preferably from 0.2:3.0. Such ratios of x:y provide the preferred vinylpyrrolidone/vinylacetate copolymers which have vinylpyrrolidone monomer to vinylacetate monomers from 0.3/2.5.

Exemplary useful vinylpyrrolidone/vinylcaprolactam/ammonium derivative terpolymers useful as the film forming constituent are comprised of vinylpyrrolidone monomers which may be represented by the following structural formula:

and vinylcaprolactam monomers which may be represented by the following structural formula:

and dimethylaminoethylmethacrylate monomers which may be represented by the following structural formula:

Exemplary vinylpyrrolidone/vinylcaprolactam/ammonium derivative terpolymer wherein the ammonium derivative monomer has 6 to 12 carbon atoms and is selected from diallylamino alkyl methacrylamides, dialkyl dialkenyl ammonium halides, and a dialkylamino alkyl methacrylate or acrylate which find use in the present inventive compositions include those marketed under the tradename ADVANTAGE® (ex. ISP.) as well as GAFFIX® (ex. ISP Corp). Such terpolymers are usually formed by a free-radical polymerization reaction to produce linear random vinylpyrrolidone/vinylcaprolactam/ammonium derivative terpolymers. The vinylpyrrolidone/vinylcaprolactam/ammonium derivative terpolymers useful in the present invention preferably comprise 17-32 weight % vinylpyrrolidone; 65-80 weight % vinylcaprolactam; 3-6 weight % ammonium derivative and 0-5 weight % stearyl methacrylate monomers. The polymers can be in the form of random, block or alternating structure having number average molecular weights ranging between about 20,000 and about 700,000; preferably between about 25,000 and about 500,000. The ammonium derivative monomer preferably has from 6 to 12 carbon atoms and is selected from the group consisting of dialkylaminoalkyl methacrylamide, dialkyl dialkenyl ammonium halide and a dialkylamino alkyl methacrylate or acrylate. Examples of the ammonium derivative monomer include, for example, dimethylamino propyl methacrylamide, dimethyl diallyl ammonium chloride, and dimethylamino ethyl methacrylate (DMAEMA). These terpolymers are more fully described in U.S. Pat. No. 4,521,404 to GAF Corporation, the contents of which are hereby incorporated by reference.

High molecular weight polyethylene glycol polymers useful in the present inventive compositions exhibit a molecular weight of at least about 100, preferably exhibits a molecular weight in the range of from about 100 to about 10,000 but most preferably a molecular weight in the range of from about 2000 to about 10,000. Particularly useful high molecular weight polyethylene glycols are available under the tradename CARBOWAX® (ex. Union Carbide Corp.). Other suppliers of high molecular weight polyethylene glycols include Ashland Chemical Co., BASF Corp., Norman, Fox & Co., and Shearwater Polymers, Inc.

Water soluble polyethylene oxides suitable for use as film forming polymers in the compositions according to the invention may be represented by the following structure:

(CH₂CH₂O)_(x)

where:

x has a value of from about 2000 to about 180,000.

Desirably, these polyethylene oxides may be further characterized as water soluble or water dispersible resins, having a molecular weight in the range of from about 100,000 to about 8,000,000. At room temperature (68° F., 20° C.) they are solids. Particularly useful as the film-forming, water soluble polyethylene oxide in the inventive compositions are POLYOX water-soluble resins (ex. Union Carbide Corp., Danbury Conn.).

Further contemplated as useful in the place of, or in combination with these polyethylene oxides are polypropylene oxides, or mixed polyethylene oxides-polypropylene oxides having molecular weights in excess of about 50,000 and if present, desirably having molecular weights in the range of from about 100,000 to about 8,000,000. According to particularly desirable embodiments of the invention, the film-forming constituent of the present invention is solely a water soluble polyethylene oxide.

Exemplary film-forming polyvinylcaprolactams include polyvinylcaprolactam compounds marketed under the tradename LUVISKOL® (ex. BASF Corp.). Such polyvinylcaprolactams may be represented by the following structural formula:

Where n has a value of at least about 500, and preferably a value in the range of from about 800 to about 1000.

Useful as the film forming constituent in the present inventive compositions are polyvinylalcohols which include those marketed under the tradename Airvol® (Air Products Inc., Allentown Pa.). These include: Airvol® 125, classified as a “super hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of at least 99.3%, and a viscosity at a 4% solution in 20° C. water of from 28-32 cps; Airvol® 165, and Airvol® 165S, each being classified as “super hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of at least 99.3%, and a viscosity at a 4% solution in 20° C. water of from 62-72 cps; Airvol® 103, classified as a “fully hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 98.0-98.8%, and a viscosity at a 4% solution in 20° C. water of from 3.5-4.5 cps; Airvol® 305, classified as a “fully hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 98.0-98.8%, and a viscosity at a 4% solution in 20° C. water of from 4.5-5.5 cps; Airvol® 107, classified as a “fully hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 98.0-98.8%, and a viscosity at a 4% solution in 20° C. water of from 5.5-6.6 cps; Airvol® 321, classified as a “fully hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 98.0-98.8%, and a viscosity at a 4% solution in 20° C. water of from 16.5-20.5 cps; Airvol® 325, classified as a “fully hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 98.0-98.8%, and a viscosity at a 4% solution in 20° C. water of from 28-32 cps; and Airvol®350, classified as a “fully hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 98.0-98.8%, and a viscosity at a 4% solution in 20° C. water of from 62-72 cps; Airvol® 425, classified as being an “intermediate hydrolyzed” polyvinylalcohol polymer classified having a degree of hydrolysis of from 95.5-96.5%, and a viscosity at a 4% solution in 20° C. water of from 27-31 cps; Airvol® 502, classified as a “partially hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 87.0-89.0%, and a viscosity at a 4% solution in 20° C. water of from 3.0-3.7 cps; Airvol® 203 and Airvol® 203S, each classified as a “partially hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 87.0-89.0%, and a viscosity at a 4% solution in 20° C. water of from 3.5-4.5 cps; Airvol® 205 and Airvol® 205S, each classified as a “partially hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 87.0-89.0%, and a viscosity at a 4% solution in 20° C. water of from 5.2-6.2 cps; Airvol® 523, classified as a “partially hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 87.0-89.0%, and a viscosity at a 4% solution in 20° C. water of from 23-27 cps; and Airvol® 540, each classified as a “partially hydrolyzed” polyvinylalcohol polymer having a degree of hydrolysis of from 87.0-89.0%, and a viscosity at a 4% solution in 20° C. water of from 45-55 cps. Of these, particularly preferred are polyvinyl alcohol polymers which exhibit a degree of hydrolysis in the range of from 87%-98% and which desirably also exhibit a viscosity at a 4% solution in 20° C. water of from 3.0-100.0 cps.

Exemplary cationic cellulose polymers which find use in the present inventive compositions as the film forming constituent include those described in U.S. Pat. No. 5,830,438 as being a copolymer of cellulose or of a cellulose derivative grafted with a water-soluble monomer in the form of quaternary ammonium salt, for example, halide (e.g., chloride, bromide, iodide), sulfate and sulfonate. Such polymers are described in U.S. Pat. No. 4,131,576 to National Starch & Chemical Company, the contents of which are hereby hydroxyethyl- and hydroxypropylcelluloses grafted with a salt of methacryloylethyltrimethyl ammonium, methacrylamidopropyltrimethyl ammonium, or dialkyldiallyl ammonium, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like. The preferred materials can be purchased for example under the trademarks “Celquat L 200” and “Celquat H 100” from National Starch & Chemical Company.

Useful cationic cellulose polymers are, per se, generally known. Exemplary cationic cellulose polymers useful in the present inventive compositions exhibit generally a viscosity of at least about 1,000 cps (as taken from a product specification of Celquat H-100; measured as 2% solids in water using an RVF Brookfield Viscometer, #2 spindle at 20 rpm and 21° C.).

A further class of materials which find use in the film forming constituent are film forming cationic polymers, an especially film-forming fatty quaternary ammonium compounds which generally conform to the following structure:

wherein R is a fatty alkyl chain, e.g., C₈-C₃₂ alkyl chain such as tallow, coco, stearyl, etc., R′ is a lower C₁-C₆ alkyl or alkylene group, the sum of both n is between 12-48, and X is a salt-forming counterion which renders the compound water soluble or water dispersible, e.g., an alkali, alkaline earth metal, ammonium, methosulfate as well as C₁-C₄ alkyl sulfates. Of these, a preferred film forming film-forming fatty quaternary ammonium compound may be represented by the following structure:

wherein R is a fatty alkyl chain, e.g., C₈-C₃₂ alkyl chain such as tallow, coco, stearyl, etc., the sum of both “n” is between 12-48, and preferably the value of each n is the same as the other, and X is a salt-forming counterion such as an alkali, alkaline earth metal, ammonium, methosulfate but is preferably an alkyl sulfate such as ethyl sulfate but especially diethyl sulfate. An preferred example of a commercially available material which may be advantageously used is CRODAQUAT TES (ex. Croda Inc., Parsippany, N.J.) described to be polyoxyethylene (16) tallow ethylammonioum ethosfulfate. A further preferred commercially available material is CRODAQUAT 1207 (ex. Croda Inc.)

A further class of particularly useful film forming materials include film-forming, organosilicone quaternary ammonium compounds. Such compounds may also exhibit antimicrobial activity, especially on hard surfaces which may supplement the effect of the quaternary ammonium surfactant compounds having germicidal properties.

Specific examples of organosilicone quaternary ammonium salts that may be used in the compositions of this invention include organosilicone derivatives of the following ammonium salts: di-isobutylcresoxyethoxyethyl dimethyl benzyl ammonium chloride, di-isobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, myristyl dimethylbenzyl ammonium chloride, myristyl picolinium chloride, N-ethyl morpholinium chloride, laurylisoquinolinium bromide, alkyl imidazolinium chloride, benzalkonium chloride, cetyl pyridinium chloride, coconut dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl diethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium bromide, di-isobutyl phenoxyethoxyethyl trimethyl ammonium chloride, di-isobutylphenoxyethoxyethyl dimethyl alkyl ammonium chloride, methyl-dodecylbenzyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, octadecyl dimethyl ethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide, octadec-9-enyl dimethyl ethyl ammonium bromide, dioctyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium iodide, octyl trimethyl ammonium fluoride, and mixtures thereof. Other water dispersible salts, such as the acetates, sulfates, nitrates, and phosphates, are effective in place of the halides, but the chlorides and bromides are preferred. The silicone group is preferably substituted with alkyl ethers. Preferred alkyl ethers are short carbon chain ethers such as methoxy and ethoxy substituents.

Still further examples of particularly preferred film-forming, organosilicone quaternary ammonium compounds which find use in the present inventive compositions include those which may be represented by the following structural representation:

wherein:

-   -   R₁ and R₂ each independently represent short chain alkyl or         alkenyl groups, preferably C₁-C₈ alkyl or alkenyl groups;     -   R₃ represents a C₁₁-C₂₂ alkyl group; and     -   X represents a salt forming counterion, especially a halogen.

Preferred short chain alkyl substituents for R₁ are methyl and ethyl, preferred short chain alkyl substituents for R₂ are straight chain links of methylene groups consisting of from 1 to 4 members, preferred R₃ substituents are straight chain links of methylene groups consisting of from 11 to 22 members, and preferred halogens for X are chloride and bromide.

Exemplary and preferred film-forming, organosilicone quaternary ammonium compounds useful in the inventive compositions is AEM® 5772 or AEM® 5700 (from Aegis Environmental Co., Midland, Mich.). Both of these materials are described as being 3-(trimethoxysilyl)propyloctadecyldimethyl ammonium chloride, AEM® 5700 and is sold as a 72% by weight active solution of the compound in a water/methanol mixture, while AEM® 5772 is sold as a 72% by weight active solution of the compound in a water/methanol mixture. While the film-forming, organosilicone quaternary ammonium compound may be present in any effective amount, desirably it is present in amounts of from 0.01-5% wt., more desirably from 0.05-2.5% wt. based on the total weight of the inventive compositions.

As further materials useful in as the film forming polymers in the present invention includes materials currently being sold under the VIVIPRINT tradename, e.g., VIVIPRINT 131, which is described to be 2-propenamide, N-[3-(dimethylamino)propyl]-2-methyl, polymer with 1-ethenyl-2-pyrrolidone hydrochloride.

One particularly preferred class of materials useful as the film forming constituent of the present invention are polynitrogen compounds, especially amphoteric polyamide polymers.

Organic polynitrogen compound in the sense of the present invention means an organic compound comprising at least 3 nitrogen atoms which are contained in the molecule in the form of an amine, like a primary, a secondary or a teriary amine, and/or in the form of an amide. By amphoteric is meant that the same compound may function as acceptor as well as a donator for protons.

Exemplary suitable functional groups imparting proton donator properties represent carboxy residues or derivatives thereof, like amides, anhydrides or esters, as well as salts thereof, like alkali salts, for example sodium or potassium salts, or ammonium salts, which may be converted into the carboxy group. Depending on the size of the polynitrogen moiety there may be one or more proton donating functionalities in the molecule. It is preferred that more than one proton donating functionalities are present in the amphoteric polynitrogen compound.

Preferred amphoteric organic polynitrogen compounds are polymeric amphoteric organic polynitrogen-compounds, having an average molecular weight of at least about 200, preferably at least about 300, 400, 500, 600, 700, 800, 900, 1000 or even greater.

The one or more amphoteric organic polynitrogen compounds preferably are independently obtainable from reacting polyalkylene polyamines, polyamidoamines, ethyleneimine-grafted polyami-doamides, polyetheramines or mixtures thereof as component A optionally with at least bi-functional cross-linking agents having a functional group independently selected from a halohydrin, a glycidyl, an aziridine or an isocyanate moiety or a halogen atom, as component B, and with monoethylenically unsaturated carboxylic acids; salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids; salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids, chlorocarboxylic acids and/or glycidyl compounds such as glycidyl acid, glycidyl amide or glycidyl esters. Such compounds are described for example in WO 2005/073357 A2, the contents of which are herein incorporated by reference.

The amphoteric organic polynitrogen compounds are obtainable by reacting components A, optionally with B and with C. The compound therefore can be present in cross-linked or uncross-linked form, wherein component A in any case is modified with component C. Components A, optionally B and C may be used in any possible ratio. If component B is employed, preferably components A and B are used in a molar ratio of from 100:1 to 1:1000, more preferred of from 20:1 to 1:20. The molar ratio of components A and C preferably is chosen such that the molar ratio of the hydrogen atoms bonded to the nitrogen in A and component C is from 1:0.2 to 1:0.95, more preferred from 1:0.3 to 1:0.9, and even more preferred from 1:0.4 to 1:0.85.

Exemplary suitable compounds useful as component A include polyalkylene polyamines, which are to be understood as referring to compounds comprising at least 3 nitrogen atoms, including but not limited to: diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexamine, diaminopropylenediamine, trisaminopropylamine and polyethyleneimine Polyethyleneimines preferably have an average molecular weight (Mw) of at least 300. It is particularly preferred that the average molecular weight of the poyethyleneimines ranges from about 600 to about 2,000,000, more preferred from 20,000 to 1,000,000, and even more preferred from 20,000 to 750,000, as may be determined by means of light scattering. The polyethyleneimines may be partially amidated, and such may be obtained by reacting polyalkylene polyamines with carboxylic acids, carboxylic acid esters, carboxylic acid anhydrides or acylhalides. The polyalkylene polyamines as suitable in the present invention preferably are amidated to an extent of 1 to 30, more preferred of up to 20% for the subsequent reactions. The amidated polyalkylene polyamines are required to contain free NH-groups in order to let them react with compounds B and C. Suitable carboxylic acids which may be used to amidate the polyalkylene polyamines are exemplified by C₁-C₂₈ carboxylic acids, including but not limited to formic acid, acetic acid, propionic acid, benzoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and behenic acid. Alternately the polyethyleneimines may be partially amidated by reacting the polyalkylene polyamine with alkyldiketene.

The polyalkylene polyamines may be used partly in quaternized form as component A. Suitable quaternization agents include, for example, alkyl halides, such as methyl chloride, ethyl chloride, butyl chloride, epichlorohydrin, hexyl chloride, dimethyl sulfate, diethyl sulfate and benzyl chloride. If quaternized polyalkyleneamines are used as component A, the degree of quaternization preferably is 1 to 30.

Further compounds which may also be used as component A included polyamidoamines. Polyamidoamines are obtainable, for example, by reacting C₄-C₁₀ dicarboxylic acids with polyalkylene polyamines containing preferably 3 to 10 alkaline nitrogen atoms. Suitable dicarboxylic acids can be exemplified by succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid and terephthalic acid. It is also possible to use mixtures of carboxylic acids, like a mixture of adipic acid and glutaric acid, or maleic acid and adipic acid. Preferably adipic acid is used to produce the polyamidoamines. Suitable polyalkylene polyamines which may be condensed with the dicarboxylic acids are similar to the ones mentioned above, and can be exemplified by diethylenetriamine, triethylenetetraamine, dipropylenetriamine, tripropylenetetraamine, dihexamethylenetriamine, aminopropyl ethylenediamine as well as bis-aminopropyl ethylenediamine. Mixtures of polyalkylene polyamines may also be used to prepare polyamidoamines. Preferably the preparation of the polyamidoamines takes place in substance, however optionally the preparation can be carried out in inert solvents. The condensation reaction of the dicarboxylic acids with the polyalkylene polyamines is carried out at elevated temperatures such as in the range of from about 120° C. to about 220° C. The water formed during the reaction is distilled off the reaction mixture. Lactones or lactams derivable from carboxylic acids having 4 to 8 carbon atoms also may be present during the condensation reaction. Generally, 0.8 to 1.4 mole of polyalkyleneamines are used with each mole of dicarboxylic acid. The thus obtained polyamidoamines have primary and secondary NH-groups and are soluble in water.

A further compound which is suitable as component A includes ethyleneimine grafted polyamidoamines. Such products are obtainable by reacting ethyleneimine with the above described polyamidoamines in the presence of Bronnstedt-acids or Lewis-acids, such as sulfuric acid, phosphoric acid or boron trifluoride etherate. Such reaction conditions result in a graft of ethyleneimine to the polyamidoamine. For example, each alkaline nitrogen group of the polyamidoamine may be grafted with 1 to 10 ethyleneimine units, i.e. 10 to 500 parts by weight of ethyleneimine are used with 100 parts by weight of a polyamidoamine

Still further compounds useful as component A include polyetheramines. Such compounds are known to the art and are described, for example, in DE-A 2916356. Polyetheramines are obtainable from condensing diamines and polyamines with chlorohydrin ethers at elevated temperatures. The polyamines may comprise up to 10 nitrogen atoms. The chlorohydrin ethers themselves can be prepared by reacting a dihydric alcohol having 2 to 5 carbon atoms, the alkoxylation products thereof having up to 60 alkyleneoxide units, glycerol or polyglycerol comprising up to 15 glycerol units, erythritol or pentaerythritol with epichlorohydrin. At least 2 to 8 moles of epichlorohydrin are reacted with each mole of said alcohol. The reaction of the diamines and the polyamines on one hand and the chlorohydrin ethers on the other hand generally takes place at temperatures of from about 1° C. to about 200° C., preferably of from 110° C. to 200° C. Moreover, polyetherpolyamines may be prepared by condensing diethanolamine or triethanolamine according to the methods known in the art, such as the methods disclosed in U.S. Pat. No. 4,404,362, U.S. Pat. No. 4,459,220 and U.S. Pat. No. 2,407,895.

Particularly preferred as component A are polyalkylene polyamines, which may be optionally are amidated up to 20%. Further preferred compounds include polyalkylene polyamines, especially polyethyleneimines, which have an average molecular weight of from about 800 to 2,000,000, more preferably from 200,000 to 1,000,000, and most preferably from 20,000 to 750,000.

Compounds suitable as component B include bifunctional cross-linking agents comprising halohydrin units, glycidyl units, aziridine units or isocyanate units or a halogen atom as functional groups.

By way of non-limiting example, suitable cross-linking agents include epihalohydrin, preferably epichlorohydrin, as well as α,ω-bis-(chlorohydrin)-polyalkylene glycol ether and the α, ω-bis-(epoxides) of polyalkylene glycol ethers which are obtainable therefrom by treatment with bases. The chlorohydrinethers may be prepared, for example, by reacting polyalkylene glycols with epichlorohydrin in a molar ratio of 1 to at least 2 to 5. Appropriate polyalkylene glycols include, for example, polyethylene glycol, polypropylene glycol and polybutylene glycol as well as block copolymers of C₂ to C₄ alkyleneoxides. The average molecular weight (Mw) of the polyalkylene glycols generally ranges from about 100 about to 6000, preferably from 300 to 2000 g/mol. α, ω-bis-(chlorohydrin) polyalkylene glycol ether are, per se, known to the art and for example are described in U.S. Pat. No. 4,144,123. Further, α,ω-dichloropolyalkylene glycols are also suitable as cross-linking agents, such as those disclosed in EP-A 0 025 515. Such α, ω-dichloropolyalkylene glycols are obtainable by reacting dihydric to tetrahydric alcohols, preferably alkoxylated dihydric to tetrahydric alcohols either with thionyl chloride resulting in a cleavage of HCI followed by catalytic decomposition of the chlorosulfonated compound while eliminating sulfur dioxide, or with phosgene resulting in the corresponding bis-chlorocarbonic acid ester while eliminating HCI, which bischlorocarbonic acid esters are catalytically decomposed eliminating carbondioxid to result in α,ω-dichloro ether. Preferably the dihydric to tetrahydric alcohols are ethoxylated and/or propoxylated glycols wherein each mole of glycol is reacted with 1 to 100, in particular with 4 to 40 moles of ethylene oxide.

Further appropriate crosslinking agent include α, ω- or vicinal dichloroalkanes, including but not limited to 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,4-dichlorobutane and 1,6-dichlorohexane. It is further to be understood that crosslinking agents which are obtainable from reacting at least trihydric alcohols with epichlorohydrin, resulting in reaction products having at least two chlorohydrin moieties may also be used. Examples for polyhydric alcohols are glycerol, ethoxylated or propoxylated glycerol, polyglycerol having 2 to 15 glycerol units within the molecule and optionally ethoxylated and/or propoxylated polyglycerol. Cross-linking agents of this kind are per se, known to the art and include those described in DE-A 2916356. Still further exemplary useful crosslinking agents include crosslinking agents containing blocked isocyanate groups such as trimethylhexamethylene diisocyanate blocked with 2,2,3,6-tetramethylpiperidone-4. Such cross-linking agents are also per se, know to the art and are described in DE-A 4028285. Moreover, crosslinking agents based on polyethers or substituted hydrocarbons containing aziridine moieties like 1,6-bis-N-aziridinohexane represent further suitable as cross-linking agents.

According to the present invention the cross-linking agents may be employed individually or as a mixture of two or more cross-linking agents. Particularly preferred are epihalohydrins, especially epichlorohydrin, α, ω-bis-(chlorohydrin)polyalkylene glycol ether, α, ω-bis-(epoxides) of polyalkylene glycol ethers and/or bisglycidylethers of polyalkylene glycols as component B.

Exemplary compounds suitable as component C include monoethylenically unsaturated carboxylic acids having preferably 3 to 18 carbon atoms in their alkenyl residue. Appropriate monoethylenically unsaturated carboxylic acids include by acrylic acid, methacrylic acid, diemethacrylic acid, ethyl acrylic acid, allyl acetic acid, vinyl acetic acid, maleic acid, fumaric acid, itaconic acid, methylene malonic acid, oleic acid and linoleic acid. Monoethylenically unsaturated carboxylic acids selected from the group comprising acrylic acid, methacrylic acid and maleic acid are especially preferred. It is also possible to use the salts of the aforementioned monoethylenically unsaturated carboxylic acids as component C. Suitable salts generally represent alkali metal, alkaline earth metal and ammonium salts of the aforementioned acids. Particularly preferred are sodium, potassium and ammonium salts. Ammonium salts can be derived from ammonia as well as from amines or amine derivatives like ethanolamine, diethanolamine and triethanolamine. Examples for alkaline earth metal salts generally represent magnesium and calcium salts of the aforementioned monoethylenically unsaturated carboxylic acids.

Exemplary suitable esters of the aforementioned monoethylenically unsaturated carboxylic acids are derivable from monohydric C₁-C₂₀ alcohols or from dihydric C₂-C₆ alcohols. Esters which may be used herein can be exemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, palmityl acrylate, lauryl acrylate, diaryl acrylate, lauryl methacrylate, palmityl methacrylate, stearyl methacrylate, dimethyl maleate, diethyl maleate, isopropyl maleate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate and hydroxyhexyl acrylate and hydroxy-hexyl methacrylate.

Representative appropriate amides of monoethylenically unsaturated carboxylic acids include acrylamide, methacrylamide and oleic amide. Suitable nitriles of the mono-ethylenically unsaturated carboxylic acids are acrylonitrile and methacrylonitrile. Further contemplated as useful amides include amides which are derivable by reacting monoethylenically unsaturated carboxylic acids, in particular (meth)acrylic acid, with amidoalkane sulfonic acids. Those amides are especially advantageous which are obtainable from reacting monoethylenically unsaturated carboxylic acids, especially (meth)acrylic acid, with amidoalkane sulfonic acids, as represented by the following formulae I or II:

H₂C═CH—X—SO₃H  (I)

H₂C═C(CH₃)—X—SO₃H  (II)

wherein X either is not present or when present is a spacing group according to one or more of the formulae: —C(O)—NH—CH_(2-n)(CH₃)_(n)(CH₂)_(m)—, —C(O)NH—, —C(O)—NH—(CH(CH₃)CH₂)— or —C(O)—NH—CH(CH₂CH₃)—, with n being 0 to 2 and m being 0 to 3. Particularly preferred are 1-acrylamido-1-propanesulfonic acid (X—C(O)—NH—CH(CH2CH3)— in formula I), 2-acrylamido-1-propanesulfonic acid (X═(O)—NH—(CH(CH3)CH2)— in formula I), 2-acrylamido-2-methyl-1-propanesulfonic acid (—C(O)—NH—C(CH3)2(CH2)— in formula I), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X≡—C(O)—NH—C(CH3)2(CH2)— in formula II) and vinylsulfonic acid (X not present in formula I).

Chlorocarboxylic acids are also appropriate as component C. Such chloro carboxylic acids include chloroacetic acid, 2-chloropropionic acid, 2-chlorobutanoic acid, dichloroacetic acid and 2,2′-dichloro propionic acid. Further compounds suitable as component C are glycidyl compounds which are represented by the following formula (III):

wherein:

X represents NH₂, OMe, OR

Me represents H, Na, K, ammonium, and

R represents C₁-C₄ alkyl or C₂-C₄ hydroxyalkyl.

Preferred compounds of formula III include but are not limited to: glycidyl acid, sodium, potassium, ammonium, magnesium or calcium salts thereof, glycidyl amide and glycidyl ester like glycidyl methyl ester, glycidyl ethyl ester, glycidyl n-propyl ester, glycidyl n-butyl ester, glycidyl iso-butyl ester, glycidyl-2-ethylhexyl ester, glycidyl-2-hydroxypropyl ester and glycidyl-4-hydroxybutyl ester. Glycidyl acid and sodium, potassium or ammonium salts thereof, or glycidyl amide are particularly preferred.

Preferably, a monoethylenically unsaturated carboxylic acid is used as component C, particularly wherein the monoethylenically unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid or maleic acid, and especially preferably wherein the monoethylenically unsaturated carboxylic acid is acrylic acid.

The above described preferred amphoteric organic polynitrogen compounds can be produced according to methods known in the art. Exemplary methods of production are disclosed for example in DE-A 4244194, in which component A at first reacts with component C and afterwards component B is added. According to the disclosure of DE-A 4244194 it is also possible to have components C and B reacted simultaneously with component A. In a preferred embodiment the amphoteric organic polynitrogen compounds comprising components A, B and C are prepared using a process comprising the following steps:

AA) cross-linking of polyalkylene polyamines, polyamidoamines, ethyleneimine-grafted polyaminoamides, polyetheramines or mixtures thereof as component A with at least bifunctional cross-linking agents having a functional group independently selected from a halohydrin, a glycidyl, an aziridine or an isocyanate moiety or a halogen atom, as component B, and

BB) reacting the product obtained in step i) with monoethylenically unsaturated carboxylic acids; salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids, chlorocarboxylic acids and/or glycidyl compounds like glycidyl acid, glycidyl amide or glycidyl esters as component C.

In step AA), the cross-linking of the compounds exemplified for component A with the cross-linking agents C proceeds according to methods known to the skilled person. Generally, the cross-linking is carried out at a temperature of from about 10° C. to about 200° C., preferably of from 30° C. to 100° C. and typically at standard pressure. The reaction times depend on the components A and B used, and in most cases range from 0, 5 to 20 hours, preferably from 1 to 10 hours. In general, curing component B is added in the form of an aqueous solution such that the reaction take place in aqueous medium as well. The product obtained can be isolated or directly used in step BBj) without further isolation which is preferred.

In step BB), the reaction product obtained in step AA) is reacted with the compound according to group C. If the compound of group C comprises a monoethylenically unsaturated compound having a double bonding system the primary or secondary amine groups of the cross-linked product obtained in step AA) are added to the free end of the double bond similar to a Michael-addition. If the compound of group C is a chlorocarboxylic acid or a glycidyl compound of formula I the reaction of the amine moieties proceeds at the chloro group or the epoxy group. The reaction typically is carried out at a temperature of from about 10° C. to about 200° C., preferably of from 30° C. to 100° C. and usually at standard pressure. The reaction time depends on the components used and generally lies within the range of from 0, 5 to 100 hours, preferably from 1 to 50 hours. It is contemplated that the foregoing reaction may take place in an aqueous solution wherein the reaction product obtained in step AA) already is present in an aqueous solution.

Specific, albeit nonlimiting examples for the preparation of such compounds are also described in WO 2005/073357 A2.

One particularly preferred compound of the amphoteric organic polynitrogen compounds as specified above, which may be used as the film forming constituent in the compositions of the present invention is presently commercially available under the trade name SOKALAN HP70 (ex. BASF AG).

Further exemplary film forming constituent useful in the compositions of the present invention include maleic acid/olefin copolymers useful as the film forming constituent of the present invention include maleic acid/olefin copolymers which may be represented by the following formula (IV):

Especially preferred are maleic acid/olefin copolymers of formula IV wherein A is selected frown the group of hydrogen, ammonium or an alkali metal; and R₁, R₂, R₃ and R₄ are each independently selected from the group of hydrogen or an alkyl group, which alkyl group may be straight or branched, saturated or unsaturated, containing from 1 to about 8 carbon atoms, preferably from 1 to about 5 carbon atoms. The monomer ratio of x to y is from about 1:5 to about 5:1, preferably from about 1:3 to about 3:1, and most preferably from 1.5:1 to about 1:1.5. The average molecular weight of the maleic acid/olefin copolymer will typically be less than about 20,000, more typically between about 4,000 and about 12,000.

A preferred maleic acid-olefin copolymer is a maleic acid-di-isobutylene copolymer having an average molecular weight of about 12,000 and a monomer ratio (x to y) of about 1:1. Such a copolymer is presently commercially available as SOKALAN CP-9, and is believed to be represented by formula IV wherein A is hydrogen or sodium, R₁ and R₃ are hydrogen, R₂ is methyl, and R₄ is neopentyl. Another preferred product is a maleic acid-trimethyl isobutylene ethylene copolymer according to formula IV wherein A is hydrogen or sodium, R₁ and R₃ are each methyl, R₂ is hydrogen and R₄ is tertiary butyl.

It is of course contemplated that a mixture or blend of two or more distinct compounds or materials may be used to provide the film forming constituent of the inventive compositions.

In addition to the film forming materials described immediately above, other film forming materials which are compatible with the balance of the constituents present in the non-liquid lavatory treatment material are also contemplated as being useful and within the scope of the present invention.

Optionally but in some cases, preferably one or more of the foregoing constituents may be provided as an encapsulated, particularly a microencapsulated material. That is to say, quantities of one or more constituents are provided covered or encapsulated in an encapsulating material. Methods suitable for such an encapsulation include the customary methods and also the encapsulation of the granules by a melt consisting e.g. of a water-soluble wax, coacervation, complex coacervation and surface polymerization. Non-limiting examples of useful encapsulating materials include e.g. water-soluble, water-dispersible or water-emulsifiable polymers and waxes. Advantageously, reactive chemical constituents, particularly the fragrance composition when present, may be provided in an encapsulated form so to ensure that they do not prematurely degrade during processing of the constituents used to form the non-liquid lavatory treatment material and that they are retained with minimal degradation in the non-liquid lavatory treatment material prior to their use. The use of water soluble encapsulating material is preferred as such will release the one or more chemical constituents when the non-liquid lavatory treatment material is contacted with water supplied either in the cistern or in the toilet bowl.

Ideally when the non-liquid lavatory treatment material is provided in such a form, the compressed solid blocks exhibit a density greater than that of water which ensures that they will sink when suspended in a body of water, e.g., the water present within a cistern. Preferably treatment blocks formed from the non-liquid lavatory treatment material exhibit a density in excess of about 1 g/cc of water, preferably a density in excess of about 1.5 g/cc of water and most preferably a density of at least about 2 g/cc of water.

When formed into compressed solid blocks, the non-liquid lavatory treatment materials according to the present invention may also be provided with a coating of a water-soluble film, such as polyvinyl acetate following the formation of the treatment blocks from the non-liquid lavatory treatment material compositions.

It will be appreciated by those of ordinary skill in the art that several of the components which are directed to provide a non-liquid lavatory treatment material composition can be blended into one chemical composition with the additional appreciation that potential blending of incompatible components will be avoided. For example, those of ordinary skill in the art will appreciate that certain anionic surfactants may have to be avoided as some may be incompatible with certain sanitizing agents and/or certain anti-lime scale agents mentioned herein. Those of ordinary skill in the art will appreciate that the compatibility of the anionic surfactant and the various sanitizing and anti-limescale agents can be easily determined and thus incompatibility can be avoided in the situations.

The non-liquid lavatory treatment material may be formed of a single chemical composition, or may formed of two (or more) different chemical compositions which may be provided as separate regions of a solid block, such as a first layer of a solid block consisting of a first chemical composition, alongside a second layer of a the solid block consisting of a second chemical composition which is different than the first chemical composition. The block may also be formed of two or more separate blocks which are simply layered or otherwise assembled, without or without the use of an adhesive. Further layers of still further different chemical compositions may also be present. Such solid blocks formed having two or more discrete layers or regions of, respectively, two or more different chemical compositions may be referred to as composite blocks.

The non-liquid lavatory treatment material may also include two or more parts, or may include two or more regions, but only one such part or region necessarily includes the first air treatment constituent in its composition. For example a non-liquid lavatory treatment material may be formed by combining a non-liquid lavatory treatment material which includes a first air treatment constituent in its composition with a further non-liquid lavatory treatment material which may exclude a further air treatment constituent in its composition, such as by pressing, coextrusion or lamination, particularly wherein the non-liquid lavatory treatment material are blocks or tablets. Alternately the two or more parts of the non-liquid lavatory treatment material may be discrete bodies of non-liquid lavatory treatment material which may merely be placed near each other without necessarily requiring physical contact with each other.

The non-liquid lavatory treatment material may also include two or more parts, or may include two or more regions, wherein a plurality of parts or regions necessarily each includes an air treatment constituent in its composition. The air treatment composition present may be the same in each of the parts or regions, or may be different air treatment compositions in different parts or regions. For example a non-liquid lavatory treatment material may be formed by combining a non-liquid lavatory treatment material which includes a first air treatment constituent in its composition with a further non-liquid lavatory treatment material which includes a further air treatment constituent (which may be the same or different) in its composition, such as by pressing, coextrusion or lamination, particularly wherein the non-liquid lavatory treatment material are blocks or tablets. Alternately the two or more parts of the non-liquid lavatory treatment material may be discrete bodies of non-liquid lavatory treatment material which may merely be placed near each other without necessarily requiring physical contact with each other. Such non-liquid lavatory treatment material may also include two or more parts, or may include two or more regions may permit for the provision of chemically incompatible air treatment constituents in a single device according to the invention. Alternately such non-liquid lavatory treatment material may also include two or more parts, or may include two or more regions may permit for the provision of devices which provide mutually exclusive air treatment benefits provided by different air treatment constituents, e.g., at least two of: perfumes, fragrances, odor masking constituents, odor counteracting constituents, odor neutralizing constituents, air sanitizing/disinfecting constituents (such as one or more glycols, and in particular triethylene glycol,) insecticides, or pesticides.

Any form of the non-liquid lavatory treatment material may also be provided with a coating film or coating layer, such as a water soluble film which is used to overwrap the chemical composition provided in the device which film provides a vapor barrier when dry, but which dissolves when contacted with water. Alternately the non-liquid lavatory treatment material may be oversprayed or dipped into a bath of a water soluble film forming constituent, and thereafter removed and thus allowing the water soluble film forming constituent to dry and form a coating layer thereon.

Exemplary materials which may be used to provide such a coating on some or all of the surfaces of the non-liquid lavatory treatment materials include one or more of the following: Rhodasurf TB-970 described by its supplier to be a tridecyl alcohol having a degree of ethoxylation of approximately 100 having an HLB of 19, and exhibiting a melting point in the range of 52-55° C.; Antarox F-108 which is described to be an EO-PO block copolymer having a degree of ethoxylation of approximately 80% and having a melting point in the range of 54-60° C.; further materials including those identified as Pluriol Z8000, and Pluriol E8000 which are believed to be optionally substituted, high molecular weight polyethylene glycols (“PEG”) having a sufficiently high molecular weight such that they have a melting point of at least 25° C., preferably a melting point of at least about 30° C. may also be used. Other water soluble materials, desirably those which have a melting point in the range of about 30-70° C., and which may be used to provide a water soluble or water dispersible coating on the non-liquid lavatory treatment material are also contemplated to be useful, especially synthetic or naturally occurring waxy materials, and high molecular weight polyalkylene glycols, especially polyethylene glycols. Certain of these coating materials may be surfactants. Generally such materials may be provided as a dispersion in water, an organic solvent or in an aqueous/organic solvent, but preferably are used as supplied from their respective supplier and are heated to at least their melting points in order to form a liquid bath. Conveniently, the non-liquid lavatory treatment materials may be affixed to the plate of a hanger are then conveniently dipped into the said bath, thereby providing a coating layer to the non-liquid lavatory treatment material. Alternately, the coating materials may be sprayed, brushed on or padded onto at least part of the surfaces of a body formed from the non-liquid lavatory treatment material.

The application of a water soluble film or coating is preferred in certain embodiments of the invention as the surface film may facilitate the handling of the non-liquid lavatory treatment material during packaging and storage prior to use of the devices of the invention. Further, the application of a water soluble film or coating is preferred as certain water soluble film former compositions may impart a desirable surface gloss to the compressed lavatory blocks.

A first exemplary non-liquid lavatory treatment material which includes a first air treatment constituent in its composition, and which is adapted to be formed into a block or tablet is described as follows:

% wt/wt. sodium dodecyl benzene sulfonate (85% 20-45% wt. actives) C₁₄/C₁₆ olefin sulfonate, sodium salt (80%) 18-30% wt. sodium lauryl ether sulfate (80%) 0-10% wt. anhydrous sodium sulfate 15-50% wt. lauryl monoenthanolamide 0-20% wt. anhydrous silica 0-2% wt. fragrance 0.001-7% wt. colorant 0-5% wt. mineral oil 0-5% wt.

A second representative non-liquid lavatory treatment material which includes a first air treatment constituent in its composition, and which is adapted to be formed into a block or tablet is described as follows:

% wt/wt. alpha olefin sulfonate, sodium salt, 95-100% wt. 12-35% wt. actives lauramide monoethanolamide, 98% wt. actives 3-33% wt. anionic surfactant, dodecylbenzene sulfonate, 12-38% wt. 80% wt. actives sodium sulfate, 100% wt. actives 12-35% wt. anionic surfactant, sodium lauryl ether sulfate, 0-10% wt. 70% wt. actives anhydrous silica, 100% wt. actives 0-10% wt. fragrance or odor masking agent 0.001-5% wt. colorant 0-5% wt.

Further representative non-liquid lavatory treatment materials which include a first air treatment constituent, and which is adapted to be formed into a block or tablet are described as follows:

A B C D E (% wt/wt) (% wt/wt) (% wt/wt) (% wt/wt) (% wt/wt) dodecyl benzene sulfonate, sodium 25 10 40 35 35 salt (80-90% active) alpha olefin sulfonate, sodium salt 25 10  5 32 32 lauryl monoethanolamide3 10  8  5 2 5 lauryl ether sulfate, sodium salt 10 — — 4.5 5 polyoxyethylene (160) 10 — — 3 — polyoxypropylene (30) glycol sodium sulfate 20 — — 21.5 21 Pluronic 87 or Pluronic88¹ — 70 50 — — C₉-C₁₁ alcohol ethoxylate, 6EO —  2 — — — fragrance or odor masking agent 0.01-3 0.01-3 0.01-3 0.01-3 0.01-3 colorant    0-1.2    0-1.2    0-1.2    0-1.5    0-1.5 silica — — — 2 2 ¹Pluronic 87 E₆₁ P_(41.5) E₆₁ -- Molecular Weight 7700 -- HLB 24 -- non-ionic surfactant Pluronic 88 E₉₈ P_(41.5) E₉₈ -- Molecular Weight 10800 -- HLB 28-- non-ionic surfactant

Yet further representative non-liquid lavatory treatment materials which include a first air treatment constituent, and which is adapted to be formed into a block or tablet are described as follows:

% w/w alpha olefin sulfonate  0-35 sodium lauryl ether sulfate 3.0-6.0 bleaching agent (e.g., DCCNa or halohydantoin) 0.5-25  lauryl monoethanolamide 2.0-5.0 dodecyl benzene sulfonate, sodium salt 50-70 Anhydrous sodium sulfate 15-25 fragrance, odor masking agent or insecticide 0.001-5    colorant   0-3.5 silica 1.0-2.0

Still further representative non-liquid lavatory treatment materials which include a first air treatment constituent as well as a film forming constituent, and which are adapted to be formed into a block or tablet are described in the following tables:

% w/w C₁₀-C₁₄benzene sulfonate, sodium salt (80% 30-38 wt. active); supplied as NANSA HS 80/PF lauryl monoethanol amide (98% wt. active) 0-7 alkene sulfonate, sodium salt; supplied as 25-40 supplied as NANSA LSS 480/H C₁₂-C₁₆ ethoxy (2-3 EO) sulfate, sodium salt 0-4 (70% wt. active); supplied as EMPICOL ESB 70 silica 0-5 sodium sulfate 15-25 3-(trimethoxysilyl)propyloctadecyldimethyl 0.05-0.4  ammonium chloride (72% wt active); supplied as AEM 5772, 72% wt. actives (ex. Aegis Environmental Co.,) citric acid 0-5 sodium bicarbonate 0-1 fragrance, odor masking agent or insecticide 0.001-5    colorant   0-3.5 deionized water   0-q.s.

% w/w C₁₀-C₁₄benzene sulfonate, sodium salt (80% wt. 25-40 actives); supplied as NANSA HS 80/PF lauryl monoethanol amide (98% wt. actives) 0-5 alkene sulfonate, sodium salt; supplied as supplied as 25-40 NANSA LSS 480/H C₁₂-C₁₆ ethoxy (2-3 EO) sulfate, sodium salt (70% wt. 0-4 actives); supplied as EMPICOL ESB 70 silica 0-5 sodium sulfate 15-25 sulfamic acid  0-15 citric acid  0-15 polyoxyethylene (16) tallow ethylammonioum 0-4 ethosfulfate (100% wt. actives); supplied as CRODAQAT TES, 100% wt. actives fragrance, odor masking agent or insecticide 0.001-5    colorant   0-3.5 d.i. water   0-q.s.

% wt/wt C₁₀-C₁₄benzene sulfonate, sodium salt (80% wt. 22-32 actives); supplied as NANSA HS 80/PF C₁₄/C₁₆ olefin sulfonate, sodium salt 30-42 (80% wt. actives); supplied as supplied as NANSA LSS 480/H sodium sulfate 20-30 lauryl monoethanol amide (98% wt. actives) 0.1-3   silica 0-2 citric acid 0.5-7   sodium lauryl ether sulfate (70% wt. actives) 0.5-4   amphoteric organic polynitrogen compound, 0.5-6   35%-35% wt. actives, supplied as SOKOLAN HP70 (ex. BASF) fragrance, odor masking agent or insecticide 0.001-5    colorant   0-3.5 d.i. water   0-q.s.

% wt/wt C₁₀-C₁₄benzene sulfonate, sodium salt (80% wt. 22-32 actives); supplied as NANSA HS 80/PF C₁₄/C₁₆ olefin sulfonate, sodium salt 30-42 (80% wt. actives); supplied as supplied as NANSA LSS 480/H sodium sulfate 20-30 lauryl monoethanol amide (98% wt. actives) 0.1-3   silica 0-2 citric acid 0.5-7   sodium lauryl ether sulfate (70% wt. actives) 0.5-4   maleic acid-di-isobutylene copolymer, 25% wt. 0.5-6   actives, supplied as SOKOLAN CP-9 (ex. BASF) fragrance, odor masking agent or insecticide 0.001-5    colorant   0-3.5 d.i. water   0-q.s.

As a further essential element the devices of the invention also necessarily include an air treatment means, which is distinguishable from and separate from the non-liquid lavatory treatment material. The air treatment means can be an article, composition or device which can be used to deliver a quantity of an air treatment constituent into the ambient environment of the laboratory appliance, and preferably wherein the laboratory appliance is a toilet bowl. The air treatment means is used to deliver a second air treatment constituent to the ambient environment which may be one or more: perfumes, fragrances, odor masking constituents, odor counteracting constituents, odor neutralizing constituents, air sanitizing/disinfecting constituents (such as one or more glycols, and in particular triethylene glycol,) insecticides, or pesticides. The second air treatment constituent may be immaterial which is the same as, or which is different than the first-year treatment constituents. Additionally, the air treatment means may be a “passive” type or “active” type.

Various examples of useful air treatment means are discussed with reference to the following figures.

Turning now to FIG. 1, there is disclosed in a perspective you a first embodiment of a device 10 according to the invention. The device is configured to be a in-the-bowl type device which is intended to be suspended from the rim of a toilet bowl,

wherein the delivery means is a cage 20 which contains within its interior 22 a non-liquid lavatory treatment material which includes a first air treatment constituent, herein the form of a longitudinal block 40 which is visible through a series of passages 24 which extend through the sidewall 26 of the cage 20. These passages 24 permit for the entry of water into the interior 22 of the cage 20, wherein it may contact block 40 in order to form a liquid treatment composition, which liquid treatment composition made an exit via the cage 20 via one or more of the series of passages 24 and be delivered to the lavatory appliance, especially a toilet bowl. Such an operation may also release a quantity of the first air treatment composition from the block 40 wherein it may be supplied to the ambient environment such as by evaporation, or entrainment in the ambient air. The device 10 further includes as air treatment means a housing 50 adapted to retain an article from which the second air treatment composition may be dispensed to the ambient environment. The housing 50 may be openable and resealable such as depicted in FIG. 1 said it would permit for the insertion of the article from which the second air treatment composition may be dispensed within its interior. Interconnecting the cage 20 and the housing 50 is a hanger 30, here in the form of a generally planar but flexible strip which is adapted to suspended the device 10 from a part of the laboratory appliance, and in particular a section of the rim of a toilet bowl such that the cage 20 is positioned within the interior of the toilet bowl and desirably wherein in the cages exposed to the path of flushing water, while the housing 50 is suspended on the exterior of the toilet bowl. In this position, the housing 50 is not expected to come into the path of flushing water, but rather is exposed to the ambient environment of the laboratory appliance. This condition persists even when the lid of the toilet seat is in a closed position, thereby permitting the continued release of the second air treatment composition to the ambient environments of the toilet bowl.

FIG. 2 depicted in a cross-sectional view the device 10 of FIG. 1, showing certain interior details. As is visible therefrom, the block 40 occupies part of the interior 22 of the cage 20. In this embodiment of the air treatment means, the housing 50 includes a top part 50 a, which it is openably connected to a bottom part 50 b. Generic representation of an article 60 from which the second air treatment composition may be dispensed is depicted as being within the interior of the housing 50.

FIGS. 3A and 3B depict in two further views the device 10 of FIGS. 1 and 2, as mounted on the rim 82 of a toilet bowl 80. In FIG. 3A, the cage 20 is seen to be suspended from and positioned by the hanger 30 such that it is positioned within the path of the flushing water represented by the arrows labeled “f”. As is visible from the figure, part of the flush water passes around the exterior of the cage 20, while part of the flush water enters into the interior of the cage 20, and subsequently exits after it has come into contact with the block 40. The quantity of the flush water which had contacted the block 40 during its transit, and dissolves at least a portion of the block 40 forms the liquid treatment composition which is useful in the treatment of the laboratory appliance. Now looking to the reverse view, which is depicted on FIG. 3B, there is visible in the housing 50 which is also suspended by the hanger 30 from the rim 82 of the toilet bowl in the city. However, the housing 50 is positioned on the exterior of the toilet bowl 80. The housing is shown to include a plurality of passages 52 which extend through the front sidewall 53 of the housing. These passages 52 provide for the inflow of, and outflow of air from the ambient environment surrounding or in the near proximity of the device 10, with the interior of the housing 50. These passages 52 also provide a flow path for the delivery of the second air treatment composition from the interior of the housing 50 to the ambient environment.

FIG. 4 depicts a further alternative embodiment of the device 10 according to the invention which includes at one end of a hanger 30 a cage 20 which includes a plurality of passages 24 passing into its interior, wherein the cage 20 is understood to contain within its interior a non-liquid lavatory treatment material although it is not visible from the figure, and at the other end of the hanger 30 a housing 50 which contains article (60, not visible) from which the second air treatment composition may be dispensed. The housing 50 also includes a plurality of passages 52 which extends through the front sidewall 53 of the housing 50, which provide a flow path for the delivery of the second air treatment composition from the interior of the housing 50 to the ambient environment.

FIGS. 5A through 5G represent various embodiments of an article 60 from which the second air treatment composition may be dispensed from the device 10. It is to be understood that any of these embodiments may be used in conjunction with anti-device 10 according to the invention and for ease of convenient reference, have been illustrated as alternative embodiments of the article 60 which may be used with the device 10 according to FIG. 4.

FIG. 5A illustrates an interior view of the housing 50 containing as the article 60 from which the second air treatment composition may be dispensed from the device 10 a container 70, having a neck 72 through which extends a porous wick 74. They container 70 includes a quantity of the second air treatment composition which may be delivered to the ambient environment by being transported outwardly from the container 70 via the porous wick 74, from whence it may be transferred such as by evaporation into the ambient air and exit the housing 50 through one or more of the passages 52.

FIG. 5B illustrates an interior view of the housing 50 containing as the article 60 from which the second air treatment composition may be dispensed, here, an electrically operated device 80 which includes a reservoir 82 containing a quantity of the second air treatment composition, a power source 84 such as one or more batteries, and a vibrating perforated elements, such as an electrically operable piezoelectric spraying device 86 which when energized causes the element oscillate, and provide a spray or missed out at the second air treatment composition into the ambient air within the housing which may then and exit the housing 50 through one or more of the passages 52.

FIG. 5C illustrates an interior view of the housing 50 containing as the article 60 from which the second air treatment composition may be dispensed, namely an aerosol or pressurized canister 90 which includes an actuator 92 which, upon operation of the actuator 92 dispenses a quantity of the second air treatment composition into the ambient air within the housing which may then and exit the housing 50 through one or more of the passages 52.

FIG. 5D illustrates an interior view of the housing 50 containing as the article 60 from which the second air treatment composition may be dispensed, here a pair of trays 100 each of which contains a quantity of a material containing the second air treatment composition which may be for example, a gel, a paste, a solid, or a fluid or liquid which may be covered with a semipermeable membrane so to ensure that the said fluid or liquid does not prematurely leak from the tray 100. The second air treatment composition emanates from the tray 100 into the ambient air within the housing which may then and exit the housing 50 through one or more of the passages 52.

FIG. 5E illustrates an interior view of the housing 50 containing as the article 60 from which the second air treatment composition may be dispensed, namely a porous article 100 such as a sheet, plate, web, pad or the like within which, or upon which, a quantity of a material containing the second air treatment composition which may be provided. The second air treatment composition emanates from the tray 100 into the ambient air within the housing which may then exit the housing 50 through one or more of the passages 52.

FIG. 5F illustrates an interior view of the housing 50 containing as the article 60 from which the second air treatment composition may be dispensed, here an electrically operated device which includes a fan 120, a power supply means here one or more batteries 122, and the downstream from the fan a perforated base 124 which has extending perpendicularly therefrom a number of elements 126 upon which, or within which is contained the second air treatment composition. The fan 120 be operated in order to provide airflow between in the number of elements 126 and thereby ensuring the second air treatment composition or induce the volatilization of the air treatment composition from the number of elements 126, from whence the second air treatment composition may then exit the housing 50 through one or more of the passages 52.

FIG. 5G illustrates an interior view of the housing 50 containing as the article 60 from which the second air treatment composition may be dispersed a particulate material, preferably a particulate material 130 such as a plurality of spheres, or beads which function as a reservoir for the second air treatment composition, and from whence they may be delivered to the ambient environment. Advantageously, such particulate materials, particularly beads may be based on a polymer or alternately, on an inner gimmick material which has absorbed therein, and/or adsorbed thereon a quantity of the second air treatment composition. Non-limiting examples of such materials include those currently marketed under the tradename Auracell® (ex. Rotuba Extruders) which are based on fragranced cellulosic polymers, as well as Polyiff® (ex. International Flavors and Fragrances Inc.), as well as Tenite® (ex. Eastman Chemical Co.).

FIGS. 6A and 6B illustrates an alternative embodiment of the air treatment means which is provided by a housing 130 mounted upon or otherwise affixable to a part of the device 10, and preferably to a part of the hanger 30, which housing 130 includes a quantity of a gel 132 in a cavity 133 which incorporates a second air treatment composition as a constituent thereof. Optionally, but in certain instances desirably, extending upwardly from the base 136 of the cavity 133 are one or more anchor elements 134 which are embedded into the gel 132. Providing such one or more anchor elements 134 provides a useful and effective means for retaining the gel 132 within that the interior of the cavity 133 so that it is not prematurely fall out from the cavity 133.

FIG. 7 is a still further embodiment of the device 10 according to the invention. As opposed to the embodiments depicted on the earlier figures, which included a specific elements or article for providing the second air treatment composition, and the embodiment according to the present figure satisfies this requirement as a part of the device 10 is molded from a so-called “fragranced polymer” which includes a quantity of an air treatment composition, preferably a fragment or a perfume. Such materials are per se, known to the art and include by way of moldable polymer compositions which include 5% or more by weight of one or more fragrancing, perfuming, odor treatment or other air treatment constituents, as well as materials previously or presently commercially available as Polyiff® (ex. International Flavors and Fragrances Inc.) and Tenite® (ex. Eastman Chemical Co.) polymers. The formation of one more elements or parts of the devices 10 according to the invention utilizing such a material may provide a continuous, and durable air treatment benefit.

FIG. 8 depicts a further embodiment of the device 10 according to the invention, here in the form of a cage-type lavatory dispensing device which includes a hanger 30 from one end of which depends a cage 20, which contains in its interior a rearward cavity 140 containing a non-liquid lavatory treatment material which includes a first air treatment constituent in its composition in the form of a compressed block, which rearward cavity includes a series of passages 24. The device 10 in intended to be installed with respect to a toilet bowl such that the rearward cavity 140 is positioned beneath or proximate to the interior toilet bowl rim and within the path of the flushing water such that, part of the flush water passes around the exterior of the cage 20, while part of the flush water enters into the rearward cavity 140 in the interior of the cage 20, and subsequently exits after it has come into contact with the block (not visible). The quantity of the flush water which had contacted the block during its transit through the rearward cavity 140 and dissolves at least a portion of the block forms the liquid treatment composition which is useful in the treatment of the laboratory appliance. The cage 20 also includes, opposite to the rearward cavity 140 a fragranced gel 132 in a cavity 133 which incorporates a second air treatment composition as a constituent thereof. Visible in this figure as extending upwardly from the base 136 of the cavity 133 are one or more anchor elements 134 which are embedded into the gel 132. Providing such one or more anchor elements 134 provides a useful and effective means for retaining the gel 132 within that the interior of the cavity 133 so that it is not prematurely fall out from the cavity 133. When the device 10 is installed in the manner described within the interior of a toilet bowl, it is to be understood that the cavity 133 as well as the gel 132 contained therein, viz, the air treatment means, is usually not in the path of the flushing water released from the rim of the toilet bowl as the dimensions of the device 10 are desirably established such that the thickness or the height of the cage 20 extends the cavity 133 and its contents beyond the normal path of flushing water. In such a manner the air treatment means may dispense the at least second air treatment composition to the ambient environment, here the interior of a toilet bowl.

FIGS. 9A and 9B depicts to alternate views of a further device 10 according to the present invention, which are in many respects similar to the device discussed with reference to FIG. 8. First with reference to FIG. 9A, depicted in a front perspective view of is a device 10 includes a cage 20, from which extends a hanger 30. Integrally formed from the front part of the cage is a cavity 133 containing a quantity of an air treatment means, here a fragranced polymer or a fragranced gel 132. Now with reference to FIG. 9B, there is illustrated a rear elevational view of the device 10 depicting in better detail the rearward cavity 140 which is spanned by a plate 142 having passing therethrough a plurality of passages 22 which permits for the entry and egress of water into the interior 24 of the rearward cavity 140 of the cage 20. Further visible within the interior 24 non-liquid lavatory treatment material which includes a first air treatment constituent in its composition in the form of a compressed block 40. The device 10 in intended to be installed with respect to a toilet bowl such that the rearward cavity 140 is positioned beneath or proximate to the interior toilet bowl rim and within the path of the flushing water such that, part of the flush water passes around the exterior of the cage 20, while part of the flush water enters into the rearward cavity 140 in the interior of the cage 20, and subsequently exits after it has come into contact with the block 40. Concurrently, it is to be understood that the cavity 133 as well as the gel 132 contained therein, viz, the air treatment means, is usually not in the path of the flushing water released from the rim of the toilet bowl as the dimensions of the device 10 are desirably established such that the thickness or the height of the cage 20 extends the cavity 133 and its contents beyond the normal path of flushing water. In such a manner the air treatment means may dispense the at least second air treatment composition to the ambient environment, here the interior of a toilet bowl.

FIGS. 10A and 10B depicts to alternate views of a further device 10 according to the present invention, wherein the device 10 is configured to be suspended from the upper rim of a toilet tank (toilet cistern) 150. The device 10 includes a hanger 30 from one end of which depends a cage 20, which contains containing a non-liquid lavatory treatment material which includes a first air treatment constituent in its composition in the form of a compressed block, which cage 20 includes a series of passages 24. The cage 24 containing the non-liquid lavatory treatment material is adapted to be suspended within the water contained in a toilet tank 150. The device 10 also includes an air treatment means comprising a housing 50 which includes a fragranced gel 132 in a cavity 133 which incorporates a second air treatment composition as a constituent thereof. Visible in this figure as extending upwardly from the base 136 of the cavity 133 are one or more anchor elements 134 which are embedded into the gel 132. Providing such one or more anchor elements 134 provides a useful and effective means for retaining the gel 132 within that the interior of the cavity 133 so that it is not prematurely fall out from the cavity 133. When installed on a toilet tank 150, as is depicted on FIG. 10B the housing 50 is positioned on the exterior of the toilet tank 150 which exposes the cavity 133 and the gel 132 to the ambient environment, allowing the second air treatment composition to be delivered to the ambient environment on the exterior of the toilet tank 150. At the same time, the cage 20 is it immersed within the water contains within the toilet tank, particularly between flush cycles thereof, causing said water to come into contact with the compressed block form of the non-liquid lavatory treatment material which is at least partially diluted or dispersed into the water, and thereby forming a lavatory treatment composition which will be released in the flush water on the next flush cycle of the toilet.

FIG. 11 depicts a “cageless” type of a device 10 according to the invention, which includes a hanger 30 having mounted on parts thereof, respectively an air treatment means in the form of a housing 50 which includes a fragranced gel 132 in a cavity 133 which incorporates a second air treatment composition as a constituent thereof, and a non-liquid lavatory treatment material which includes a first air treatment constituent in its composition in the form of a compressed block 40 which is attached directly to the hanger 30 great visibly absent from the depicted device 10 is a cage, or other container surrounding the block 40. It is to be understood that the composition of the block 40 is such that it may be directly affixed to a portion of the anger 30 without requiring an enclosing, or encasing element or body. The device 10 in intended to be installed with respect to a toilet bowl such that the end of the hanger 30 is extended to grasp at least part of a toilet bowl rim such that the block 40 is positioned beneath or proximate to the interior toilet bowl rim and within the path of the flushing water such that, part of the flush water passes around the block 40. Further, concurrently the air treatment means may dispense the at least second air treatment composition to the ambient environment, here the interior of the toilet bowl as it is to be understood that the cavity 133 as well as the gel 132 contained therein, viz, the air treatment means, is usually not in the path of the flushing water released from the rim of the toilet bowl and its position on the hanger 30 normally places it in a location beyond the normal path of flushing water. Advantageously, the housing 50 comprising the cavity 133 as well as the gel 132 contained therein is positioned to be adjacent to or abutting the inner side wall of the toilet bowl rim, and above the normal path of water being flushed from the underside of the rim.

FIGS. 12A, 12B and 12C all depict in a frontal perspective views three similar embodiments of a further device 10 according to the present invention.

First with respect to FIG. 12A, the device 10 includes a hanger 30 (shown in phantom for sake of clarity) having suspended thereon a housing 50 which includes as air treatment means a fragranced gel 132 in a cavity 133 which incorporates a second air treatment composition as a constituent thereof, and the device 10 further includes a cage 20 which contains within its interior 22 a non-liquid lavatory treatment material which includes a first air treatment constituent, herein the form of a longitudinal block 40 which is visible through a series of passages 24 which extend through the sidewall 26 of the cage 20. These passages 24 permit for the entry of water into the interior 22 of the cage 20, wherein it may contact block 40 in order to form a liquid treatment composition, which liquid treatment composition made an exit via the cage 20 via one or more of the series of passages 24 and be delivered to the lavatory appliance, especially a toilet bowl. Such an operation may also release a quantity of the first air treatment composition from the block 40 wherein it may be supplied to the ambient environment such as by evaporation, or entrainment in the ambient air. Concurrently with the release of the first air treatment composition, the second air treatment composition may be dispensed to the ambient environment from the housing 50. The device 10 further includes at ends 21, 23 thereof further housings 50 a, 50 b which include in their interior is yet further air treatment composition which can be the same as, or different than the first air treatment composition or the second air treatment composition. Indeed, the air treatment composition separately contained in the further housings 50 a, 50 b maybe this the same as or different from one another. The further housings 50 a, 50 b include respective passages 52 which extend through the front sidewall 53 of the housing. These passages 52 provide for the inflow of, and outflow of air from the ambient environment surrounding or in the near proximity of the device 10, with the interior of the further housings 50 a, 50 b. These passages 52 also provide a flow path for the delivery of the second air treatment composition from the interior of the further housings 50 a, 50 b to the ambient environment. The device 10 in intended to be installed with respect to a toilet bowl such that the cage 20 containing the block 40 is positioned beneath or proximate to the interior toilet bowl rim and within the path of the flushing water such that, part of the flush water passes contacts the block 40, thus forming a treatment composition which can then be dispensed to the interior of the toilet bowl. Concurrently, the housing 50 is usually not in the path of flush water, and thus may dispense the second air treatment composition to the ambient environment, here the interior of the toilet bowl. Further concurrently, the further air treatment composition's present within the further housings 50 a, 50 b may also release and deliver their air treatment materials to the ambient environment as well, even though they are in the path of flushing water.

With respect now to FIG. 12B, the device 10 includes in further housings 50 a, 50 b at the ends of the cage 20 as air treatment means a fragranced gel 132 in respective cavities 133 a, 133 b which incorporates a second (and optionally further) air treatment composition as a constituent thereof. Within the interior 22 of the cage 20 the device 10 further includes a non-liquid lavatory treatment material which includes a first air treatment constituent, herein the form of a longitudinal block 40 which is visible through a series of passages 24 which extend through the sidewall 26 of the cage 20. These passages 24 permit for the entry of water into the interior 22 of the cage 20, wherein it may contact block 40 in order to form a liquid treatment composition, which liquid treatment composition may exit via the cage 20 via one or more of the series of passages 24 and be delivered to the lavatory appliance, especially a toilet bowl. Simultaneously the second (and optionally further) air treatment composition may emanate from the cavities 133 a, 133 b into the ambient environment. Optionally, but preferably a hanger is also included as part of the device 10, in a manner similar to that discussed with reference to the following FIG. 12C although such has been omitted in the depiction of the present embodiment.

FIG. 12C illustrates an embodiment of the device 10 which closely corresponds to that discussed with reference to FIG. 12A, but differs only in the omission of the housing which includes as air treatment means a fragranced gel in a cavity which incorporates a second air treatment composition as a constituent thereof, but which for all other purposes includes the same elements, and functions in the same manner as discussed with reference to FIG. 12A.

While the invention is susceptible of various modifications and alternative forms, it is to be understood that specific embodiments thereof have been shown by way of example in the drawings which are not intended to limit the invention to the particular forms disclosed; on the contrary the intention is to cover all modifications, equivalents and alternatives falling within the scope and spirit of the invention as expressed in the appended claims. 

1. A device adapted to be used with a toilet bowl for delivering a treatment composition thereto comprising: a delivery means which comprises a non-liquid lavatory treatment material which includes a first air treatment constituent, which material forms an aqueous treatment composition when the non-liquid lavatory treatment material is contacted with water being flushed within a toilet bowl; and, a further air treatment means containing a further air treatment constituent which is separate from the non-liquid lavatory treatment material which includes the first air treatment constituent for providing a further air treatment constituent to the ambient environment of the device.
 2. The device according to claim 1 wherein: the delivery means is a cage or container containing a quantity of a non-liquid lavatory treatment material which in addition to the first air treatment constituent also contains one or more surfactants, wherein an aqueous treatment composition providing a cleaning and/or sanitizing and/or disinfecting benefit to lavatory appliance is formed by contacting the lavatory treatment material with water.
 3. The device according to claim 1 wherein: the non-liquid lavatory treatment material is a solid, a gel, or a paste.
 4. The device according to claim 1 wherein: the non-liquid lavatory treatment material exhibits a viscosity of at least 1000 cps.
 5. (canceled)
 6. The device according to claim 1 wherein the first air treatment constituent comprises one or more constituents selected from: perfumes, fragrances, odor masking constituents, odor counteracting constituents, odor neutralizing constituents, air sanitizing/disinfecting constituents (such as one or more glycols, and in particular triethylene glycol) insecticides, or pesticides.
 7. The device according to claim 1 wherein the further air treatment constituent of the air treatment means comprises one or more constituents selected from: perfumes, fragrances, odor masking constituents, odor counteracting constituents, odor neutralizing constituents, air sanitizing/disinfecting constituents (such as one or more glycols, and in particular triethylene glycol) insecticides, or pesticides.
 8. (canceled)
 9. A process for providing both a cleaning and/or sanitizing and/or disinfecting treatment to a toilet bowl and to also provide a treatment of the ambient environment in the proximity of the toilet bowl being treated, which process includes the step of providing a device according to claim 1, and mounting the device upon a rim of a toilet bowl whereby the non-liquid lavatory treatment material which includes a first air treatment which material forms an aqueous treatment composition when the non-liquid lavatory treatment material is contacted with water being flushed within a toilet and, a further air treatment means containing a further air treatment constituent which is separate from the non-liquid lavatory treatment material which includes the first air treatment constituent for providing a further air treatment constituent to the ambient environment of the device. 